Co-reporter:Tong-Ying Chang, Bing-Ping Yang, Chun-Li Hu, Dong Yan, and Jiang-Gao Mao
Crystal Growth & Design September 6, 2017 Volume 17(Issue 9) pp:4984-4984
Publication Date(Web):August 16, 2017
DOI:10.1021/acs.cgd.7b00924
The first series of metal phosphate iodates, namely, M(IO3)(HPO4)(H2O) (M = Sc 1, Fe 2, Ga 3, In 4), have been obtained through hydrothermal syntheses. The title compounds are isomorphic and crystallize in the monoclinic space group C2/c (No. 15). Their structures feature a three-dimensional (3D) network composed of 1D [M(HPO4)(H2O)]+ chains that are further bridged by IO3 groups, forming 1D tunnels based on eight-membered rings along the b-axis. Magnetic measurements revealed antiferromagnetic coupling interactions between magnetic centers in compound 2. The UV absorption spectra measurements revealed that compound 2 exhibits a broad absorption peak at about 427 nm. The TGA studies and IR spectra for compounds 1–4 were also performed.
Co-reporter:Fei-Fei Mao, Chun-Li Hu, Bing-Xuan Li, and Jiang-Gao Mao
Inorganic Chemistry November 20, 2017 Volume 56(Issue 22) pp:14357-14357
Publication Date(Web):November 9, 2017
DOI:10.1021/acs.inorgchem.7b02508
Partial substitution of iodate anions in La(IO3)3 by OH– or NO3– anion led to acentric La3(IO3)8(OH) and chiral La(IO3)2(NO3). The structure of La3(IO3)8(OH) can be seen as a complex three-dimensional (3D) network composed of two-dimensional [La3(IO3)2(OH)]6+ cationic layers that are further bridged by remaining iodate anions, or alternatively as a 3D network composed of one-dimensional [La3(IO3)6(OH)]2+ cationic columns being further interconnected by additional iodate anions, while the structure of La(IO3)2(NO3) can be seen as a novel 3D structure with planar NO3 groups serving as linkage between the [La3(IO3)6]3+ triple layers. Compared to La(IO3)3, both compounds show considerably wide band gaps and enhanced thermal stability. La(IO3)2(NO3) shows a moderate second harmonic generation (SHG) response of ∼0.6 times that of KDP (KH2PO4), a wide band gap of 4.23 eV, and a high LDT value (22 × AgGaS2). Optical property measurements, thermal analysis, as well as theoretical calculations on SHG origin, were performed. It can be deduced that partial substitution of iodate anions can be a facile route to design new noncentrosymmetric metal iodates with novel structure and potential application.
Co-reporter:Jiang-He Feng, Chun-Li Hu, Hou-Ping Xia, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry December 4, 2017 Volume 56(Issue 23) pp:14697-14697
Publication Date(Web):November 13, 2017
DOI:10.1021/acs.inorgchem.7b02670
Here, the combination of the strong electropositive lithium and the most electronegative fluorine with the TeO3 group afforded the first lithium fluoride tellurite, namely, Li7(TeO3)3F (P63), which was synthesized by solid-state reactions. Its structure features a novel three-dimensional anionic framework of [Li7O9F]12– composed of LiO3F and LiO4 tetrahedra with one-dimensional hexagonal tunnels of 12-membered rings along the c-axis, filled by the “isolated” ψ-TeO3 tetrahedra. Notably, this compound displays the largest band gap of 4.75 eV among all of the non-centrosymmetric metal-tellurites reported so far, as well as strong second harmonic generation (SHG) responses (3 × KH2PO4 @1064 nm, 0.2 × β-BaB2O4 @532 nm) and a large laser damage threshold (73 × AgGaS2). Furthermore, theoretical calculations reveal that the LiO4 and LiO3F tetrahedra also contribute significantly to the SHG response (∼30%).
Co-reporter:Tong-Ying Chang, Chun-Li Hu, Dong Yan, Jiang-Gao Mao
Journal of Solid State Chemistry 2017 Volume 251(Volume 251) pp:
Publication Date(Web):1 July 2017
DOI:10.1016/j.jssc.2017.04.008
•Two new phosphates, (H3O)Ca2Zn3.5(PO4)4 and Ba2Cd3(PO4)2(HPO4)2 have been prepared by hydrothermal reactions.•(H3O)Ca2Zn3.5(PO4)4 crystallizes in the noncentrosymmetric space group P−421c and displays a weak SHG response.•Luminescent studies suggest that (H3O)Ca2Zn3.5(PO4)4 emits blue light.•The UV cut-off edge of title compounds are around at 218 nm.•The theoretical calculations of (H3O)Ca2Zn3.5(PO4)4 and Ba2Cd3(PO4)2(HPO4)2 based on DFT methods were performed.Two new phosphates, non-centrosymmetric (NCS) (H3O)Ca2Zn3.5(PO4)4 and centrosymmetric (CS) Ba2Cd3(PO4)2(HPO4)2 have been prepared by hydrothermal reactions. The single-crystal X-ray structural analyses have shown that they crystallized in space group P−421c and P21/c, respectively·(H3O)Ca2Zn3.5(PO4)4 features a three-dimensional (3D) network structure composed of ZnO4 and PO4 tetrahedra that are interconnected via corner-sharing, forming 1D channels of 6-MRs and 8-MRs which are filled by Ca2+ and H3O+ cations, respectively. Ba2Cd3(PO4)2(HPO4)2 features a layered [Cd3(PO4)2(HPO4)2]4- composed of 1D chain of edge-sharing CdO6 octahedra that are further bridged by PO4 tetrahedra with Ba2+ cations filling the interlayer spaces. Luminescent studies suggest that (H3O)Ca2Zn3.5(PO4)4 emits blue light. Optical diffuse reflectance spectra show the experimental band gaps for (H3O)Ca2Zn3.5(PO4)4 and Ba2Cd3(PO4)2(HPO4)2 are 5.67 eV and 5.68 eV, respectively. The UV cut-off edge of title compounds are around at 218 nm·(H3O)Ca2Zn3.5(PO4)4 exhibits a very weak SHG response.Non-centrosymmetric (H3O)Ca2Zn3.5(PO4)4 with a novel 3D network structure and centrosymmetric (CS) Ba2Cd3(PO4)2(HPO4)2 with a 2D layered structure are shown in the figure.Download high-res image (182KB)Download full-size image
Co-reporter:Dong Yan;Fei-Fei Mao;Ting-Ting Ruan
Dalton Transactions 2017 vol. 46(Issue 22) pp:7361-7368
Publication Date(Web):2017/06/06
DOI:10.1039/C7DT01360D
Two novel tartratoborates, namely, K2[(C4H2O6)(B3O4H)](H2O) (1) and KCu2[(C4H2O6)2B](H2O)2.5 (2), have been successfully synthesized by solvothermal reactions. They feature different kinds of structural types based on hybrid borate–tartrate motifs. The structure of compound 1 features a 3D network composed of novel [(C4H2O6)2(B3O4H)2]4− anionic groups interconnected by K+ cations. The [(C4H2O6)2(B3O4H)2]4− anion was formed by the condensation of two (B3O8H)6− groups and two tartrate anions, and such condensation reaction has never been reported previously. Compound 2 exhibits a novel 3D network structure in which 2D {Cu2[(C4H2O6)2B](H2O)2}− layers are further interconnected via K+ ions. The [(C4H2O6)2B]5− anion was formed by the condensation of two tartrate anions with a B(OH)4− unit. Magnetic measurements reveal a dominant antiferromagnetic interaction between neighboring Cu2+ ions in compound 2. Furthermore, UV-vis and infrared spectra and thermal analyses were also performed.
Co-reporter:Ming-Li Liang; Chun-Li Hu; Fang Kong
Journal of the American Chemical Society 2016 Volume 138(Issue 30) pp:9433-9436
Publication Date(Web):July 18, 2016
DOI:10.1021/jacs.6b06680
The first bismuth selenite fluoride, BiFSeO3, was obtained by aliovalent substitution of 2D BiOIO3. Its structure features a 3D network composed of 1D [BiF]2+ chains interconnected by SeO3 groups. BiFSeO3 exhibits a very strong second harmonic generation (SHG) effect of about 13.5 times that of KH2PO4 (KDP) under 1064 nm laser radiation and 1.1 times that of KTiOPO4 (KTP) under 2.05 μm laser radiation, which is the highest among all of the metal selenites reported. It has also very simple chemical composition and can be synthesized easily under mild hydrothermal conditions.
Co-reporter:Hui Yang, Chun-Li Hu, and Jiang-Gao Mao
Inorganic Chemistry 2016 Volume 55(Issue 12) pp:6051-6060
Publication Date(Web):June 6, 2016
DOI:10.1021/acs.inorgchem.6b00584
The first examples of mixed-anion lanthanide galloborates, namely, Ln2Ga[B3O6(OH)]2[B7O9(OH)2](CH3CO2)2 [Ln = Y (1), Sm (2), Eu (3), Gd (4), Dy (5)], have been obtained through hydrothermal synthesis. The title compounds are isomorphic and belong to monoclinic space group C2/c (No. 15). Their structures possess [B7O13(OH)2] borate layers further bridged with [B3O7] clusters to give a three-dimensional (3D) borate framework displaying two types of rhombus-like B14O14 14-membered-ring (14-MR) channels along the b axis. The Ga3+ ions are octahedrally coordinated and located at one end of the B14O14 14-MR channels, forming small tunnels of B7Ga 8-MRs, which are filled by the LnIII ions. The Ln ions and Ga cations are further held together by bridging acetate anions. It is worth noting that in these compounds there are two different types of borate clusters and two types of anions that are uncommon in the borates reported. Luminescent studies revealed the characteristic emission bands of Ln ions for compounds 2–5, and the luminescent lifetimes are 3.6, 0.86, and 3.05 ns for compounds 2, 3, and 5, respectively. Magnetic measurements suggest that there are antiferromagnetic interactions between magnetic centers for compounds 2–5.
Co-reporter:Dong Yan, Fei-Fei Mao, and Jiang-Gao Mao
Inorganic Chemistry 2016 Volume 55(Issue 20) pp:10558-10566
Publication Date(Web):September 30, 2016
DOI:10.1021/acs.inorgchem.6b01790
A series of lanthanide boroantimonates, namely, LnBSb2O8 (Ln = Sm 1, Eu 2, Gd 3, and Tb 4) have been successfully synthesized by high temperature solid-state reactions for the first time. They are isostructural and feature novel three-dimensional (3D) frameworks composed of 2D [Sb3O12]9– layers interconnected by 1D [SbBO7]6– chains with remaining BO3 groups hanging on the walls of the 1D 6-membered-ring (MR) tunnels along the a-axis, and the lanthanide ions filled in the voids of the anionic structure. They exhibit high thermal stability (up to 900 °C). Luminescent studies suggest that compounds 1, 2, and 4 have potential application as orange, red, and green light luminescent materials, respectively. Magnetic measurements reveal ferromagnetic coupling interactions in compound 3 and antiferromagnetic coupling interactions between magnetic centers in compounds 1, 2, and 4.
Co-reporter:Fang Kong; Chun-Li Hu; Ming-Li Liang
Inorganic Chemistry 2016 Volume 55(Issue 2) pp:948-955
Publication Date(Web):December 21, 2015
DOI:10.1021/acs.inorgchem.5b02523
The first example of SHG crystal in the metal bromates containing π-conjugated planar triangle systems, namely, Pb4(OH)4(BrO3)3(NO3), was successfully synthesized via the hydrothermal method. Furthermore, a single crystal of centrosymmetric Pb8O(OH)6(BrO3)6(NO3)2·H2O was also obtained. Both compounds contain similar [Pb4(OH)4] cubane-like tetranuclear clusters, but they display different one-dimensional (1D) chain structures. Pb4(OH)4(BrO3)3(NO3) features a zigzag [Pb4(OH)4(BrO3)3]+ 1D chain, while Pb8O(OH)6(BrO3)6(NO3)2·H2O is composed of two different orthogonal chains: the linear [Pb4(OH)4(BrO3)2]2+ 1D chain along the b-axis and the zigzag [Pb4O2(OH)2(BrO3)4]2– 1D chain along the a-axis. The NO3 planar triangles of the compounds are all isolated and located in the spaces of the structures. Pb4(OH)4(BrO3)3(NO3) exhibits the first example of SHG crystal in the metal bromates with π-conjugated planar triangle. The second-harmonic generation (SHG) efficiency of Pb4(OH)4(BrO3)3(NO3) is approximately equal to that of KDP and it is phase-matchable. Dipole moment and theory calculations indicate that BrO3, NO3, and PbO4 groups are the origin of its SHG efficiency, although some of the contributions cancel each other out.
Co-reporter:Bing-Ping Yang, Chun-Li Hu, Xiang Xu, and Jiang-Gao Mao
Inorganic Chemistry 2016 Volume 55(Issue 5) pp:2481-2487
Publication Date(Web):February 5, 2016
DOI:10.1021/acs.inorgchem.5b02859
A new series of platinum iodates, namely, α-(H3O)2Pt(IO3)6, β-(H3O)2Pt(IO3)6, and A2Pt(IO3)6 (A = Na, K, Rb, Cs), have been synthesized. Interestingly, among these six stoichiometrically identical compounds, α-(H3O)2Pt(IO3)6 is polar, whereas other compounds are nonpolar and centrosymmetric. They all consist of zero-dimensional [Pt(IO3)6]2– molecular units separated by H3O+ or A+ cations. All of the lone electron pairs of the IO3– groups are aligned and almost point to one direction for α-(H3O)2Pt(IO3)6, whereas IO3– groups are located trans to each other in other compounds. The material, α-(H3O)2Pt(IO3)6, exhibits very strong second harmonic generation (SHG) effects, approximately 1.2 × KTiOPO4 (KTP), and is phase-matchable. Thermogravimetric analysis, elemental analysis, infrared spectra, UV–vis spectra, nonlinear optical properties, and theoretical calculations are also reported.
Co-reporter:Qian Qian, Fang Kong and Jiang-Gao Mao
RSC Advances 2016 vol. 6(Issue 83) pp:79681-79687
Publication Date(Web):18 Aug 2016
DOI:10.1039/C6RA17867G
Systematic explorations of new phases in the Ag+–Ti4+/Zr4+/Nb5+/Ta5+–Se4+–O(F) system by hydrothermal syntheses or standard high temperature solid-state reactions resulted in four new mixed-metal silver selenites, namely, Ag3Ti3O3(SeO3)4F (1, P63), Ag2ZrF2(SeO3)2 (2, Cmca) and AgMO(SeO3)2 (M = Nb, 3; Ta, 4) in the space group Cmcm. Ag3Ti3O3(SeO3)4F features an interesting [Ti3O3(SeO3)4]2− 3D anionic framework composed of 1D chains of corner-sharing TiO6 octahedra which are further interconnected by tridentate bridging SeO32− anions, displaying 1D hexagonal channels of Ti6Se6 12-member rings (MRs) along the c-axis, filled by the Ag+ cations and isolated F− anions. More interestingly, it displays a moderate strong Second-Harmonic Generation (SHG) response about 2 times that of KH2PO4 (KDP). Compound 2 features a novel 1D [ZrF2(SeO3)2]2− anionic chain composed of edge-sharing ZrO4F4 polyhedra in which two neighboring Zr4+ cations are further bridged by a pair of selenite anions. Compounds 3 and 4 are isostructural and their structures feature 1D anionic chains of [MO(SeO3)2]− (M = Nb, Ta) which are separated by Ag+ cations, the 1D [MO(SeO3)2]− (M = Nb, Ta) chain is formed by 1D chains of corner-sharing MO6 (M = Nb, Ta) octahedra in which two neighboring metal centers are also bridged by a pair of selenite anions. Other characterizations including thermal analyses, optical and luminescence property measurements have also been performed.
Co-reporter:Dr. Xiang Xu;Dr. Chun-Li Hu;Bing-Xuan Li;Dr. Jiang-Gao Mao
Chemistry - A European Journal 2016 Volume 22( Issue 5) pp:1750-1759
Publication Date(Web):
DOI:10.1002/chem.201504117
Abstract
Two new polar potassium gold iodates, namely, K2Au(IO3)5 (Cmc21) and β-KAu(IO3)4 (C2), have been synthesized and structurally characterized. Both compounds feature zero-dimensional polar [Au(IO3)4]− units composed of an AuO4 square-planar unit coordinated by four IO3− ions in a monodentate fashion. In β-KAu(IO3)4, isolated [Au(IO3)4]− ions are separated by K+ ions, whereas in K2Au(IO3)5, isolated [Au(IO3)4]− ions and non-coordinated IO3− units are separated by K+ ions. Both compounds are thermally stable up to 400 °C and exhibit high transmittance in the NIR region (λ=800–2500 nm) with measured optical band gaps of 2.65 eV for K2Au(IO3)5 and 2.75 eV for β-KAu(IO3)4. Powder second-harmonic generation measurements by using λ=2.05 μm laser radiation indicate that K2Au(IO3)5 and β-KAu(IO3)4 are both phase-matchable materials with strong SHG responses of approximately 1.0 and 1.3 times that of KTiOPO4, respectively. Theoretical calculations based on DFT methods confirm that such strong SHG responses originate from a synergistic effect of the AuO4 and IO3 units.
Co-reporter:Chun-Li Hu, Jiang-Gao Mao
Coordination Chemistry Reviews 2015 Volume 288() pp:1-17
Publication Date(Web):1 April 2015
DOI:10.1016/j.ccr.2015.01.005
•Recent advances on second order NLO materials based on metal iodates are reviewed.•Under suitable conditions, IO3 and IO4 groups are able to be polymerized.•Combination of two types of lone pair cations afforded many new polar materials.•The d0-TMO6 octahedra can be combined with iodate groups to form new SHG compounds.•Square planar TMO4 units can be used to form polar metal iodates.Metal iodates with a lone-pair containing I(V) in an asymmetric coordination geometry can form a diversity of unusual structures, including non-centrosymmetric (NCS) structures with promising second-order nonlinear optical (NLO) properties. They have wide transparent wavelength regions (0.4–12 μm), large second harmonic generation (SHG) coefficients (>10 × KDP for many iodates) and high optical-damage thresholds (4–50 GW cm−2) as well as good thermal stability (usually >400 °C). In this review, the structures and second-order NLO properties of metal iodates will be discussed. Under reaction media with a high concentration of iodic acid, the iodate groups can be condensed into binuclear or polynuclear iodate anions, these compounds are able to display large SHG responses. The introduction of other lone pair containing cations into the iodate system is also an effective strategy to design new NCS materials. The combination of d0 transition-metal cations with iodate groups afforded a large number of NCS metal iodates with anionic structures ranging from 0D clusters, 1D chains, 2D layers to 3D networks. These NCS materials can display excellent second-order NLO properties when the polarizations from both types of the asymmetric units are aligned properly. As for the iodates of d8-transition metal ion with a square planar TMO4 geometry, the cis TM(IO3)4 unit in which the four iodate groups are located at the same side of the TMO4 plane favors the formation of NCS structures whereas the trans- one in which the four iodate groups being located at both sides of the TMO4 square plane prefers to a centrosymmetric structure. NCS structures with good SHG properties can also be found in other mixed metal iodate systems.Metal iodates with a lone-pair containing I(V) in an asymmetric coordination geometry can form a diversity of unusual structures, including non-centrosymmetric (NCS) or polar structures with promising second order NLO properties. They have wide transparent wavelength regions, large second-harmonic-generation (SHG) coefficients and high optical-damage thresholds as well as good thermal stability. In this review, the structures and second-order NLO properties of metal iodates will be discussed. The synthetic routes for new SHG materials based on metal iodates include the condensation of iodate groups into SHG active polyiodate anions, the introduction of other lone pair containing cations, octahedrally coordinated d0 transition-metal cations and the d8-transition metal ion with a square planar TMO4 geometry into the metal iodate systems.
Co-reporter:Jiang-He Feng, Chun-Li Hu, Xiang Xu, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry 2015 Volume 54(Issue 5) pp:2447-2454
Publication Date(Web):February 18, 2015
DOI:10.1021/ic503068s
The first examples of metal borotellurates, namely, Na2RE2TeO4(BO3)2 (RE = Y, Dy–Lu) have been prepared by using solid-state reactions. They possess similar structures and crystallize in space group P21/c (No. 14). These compounds feature a novel [RE2TeO4(BO3)2]2– 3D network structure composed of linear [TeO4(BO3)2]8– anions interconnected by RE3+ ions with the voids of the network filled by the Na+ ions. They exhibit high thermal stability (higher than 800 °C). Results of magnetic measurements on Dy, Ho, and Er compounds indicate that they display weak antiferromagnetic interaction between RE(III) centers. Luminescent studies show that Na2Er2TeO4(BO3)2 has a strong emission at 1.562 μm with a wide fwhm (70 nm) and moderate lifetime (0.18 ms), whereas Na2Yb2TeO4(BO3)2 has a strong NIR region emission around 1.02 μm. Furthermore, UV–vis-NIR absorption spectra, infrared spectra, and DFT calculations for the Y compound as a representative were also accomplished.
Co-reporter:Yuan Lin; Chun-Li Hu
Inorganic Chemistry 2015 Volume 54(Issue 21) pp:10407-10414
Publication Date(Web):October 21, 2015
DOI:10.1021/acs.inorgchem.5b01848
Two new mixed metal fluoride carbonates, KCdCO3F and K2Pb3(CO3)3F2, have been synthesized by solvothermal and solid-state techniques. KCdCO3F crystallizes in the acentric nonpolar space group P6̅m2, and its structure features a three-dimensional anionic framework in which the CdCO3 layers are further interconnected by bridging F– anions with the negative charge balanced by K+ cations. K2Pb3(CO3)3F2 crystallizes in the centrosymmetric space group P63/mmc, and its structure exhibits a layered anionic skeleton featuring corner-shared PbO6F and PbO6F2 polyhedra. UV–vis diffuse reflectance spectroscopy studies show that the short-wavelength absorption edges of KCdCO3F and K2Pb3(CO3)3F2 are 227 and 287 nm, respectively. The second harmonic generation (SHG) measurement reveals that KCdCO3F is a phase-matchable material for generation of doubled-frequency light at both 532 and 266 nm, with a large SHG response of approximately 5.2 times that of KH2PO4 (KDP) at 532 nm and a moderate SHG response of approximately 0.75 times that of β-BaB2O4 (BBO) at 266 nm. Therefore, it is a promising UV material for fourth harmonic generation on a 1064 nm Q-switched Nd:YAG laser.
Co-reporter:Xue-Li Cao, Chun-Li Hu, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry 2015 Volume 54(Issue 8) pp:3875-3882
Publication Date(Web):April 2, 2015
DOI:10.1021/acs.inorgchem.5b00052
Two new cesium selenites containing TaO6 or TiO4F2 octahedra, namely, Cs(TaO2)3(SeO3)2 (1) and Cs(TiOF)3(SeO3)2 (2), have been prepared using standard high temperature solid-state method and hydrothermal reaction, respectively. Compound 1 crystallizes in P3̅m1 and features an unusual [(TaO2)3(SeO3)2]− sandwich-like double layer in which two [Ta(1)O3(SeO3)]3– layers are bridged by central Ta(2)O6 octahedra via corner-sharing, whereas Cs(TiOF)3(SeO3)2 with a polar space group P63mc features an interesting hexagonal tungsten oxide (HTO) layered topology and presents a strong second harmonic generation (SHG) of about 5 × KDP (KH2PO4), which is much larger than those of A(VO2)3(QO3)2 (A = K, Tl, Rb, Cs, or NH4; Q = Se, Te) with a similar HTO layered structure. Cs(TiOF)3(SeO3)2 is also type-I phase matching. The SHG of above-mentioned HTO materials can be enhanced greatly with the replacement of VO6 octahedra by TiO4F2 octahedra. Furthermore, thermal stabilities, UV–vis diffuse reflectance spectra, infrared spectra, relationship between crystal structure and SHG, and theoretical calculations were also reported.
Co-reporter:Hui Yang; Chun-Li Hu; Xiang Xu
Inorganic Chemistry 2015 Volume 54(Issue 15) pp:7516-7523
Publication Date(Web):July 21, 2015
DOI:10.1021/acs.inorgchem.5b01126
The first examples of lanthanide borate–acetate mixed anion compounds, namely, Ln2(CH3CO2)2[B5O9(OH)]·H2O (Ln = La 1; Ce 2; Pr 3), were synthesized under hydrothermal conditions. These compounds are isostructural and crystallize in polar space group Cc. They display a unique three-dimensional (3D) framework built by a 3D network of lanthanide borate further decorated by acetate anions. The borate anion exhibits a 2D layer in the ac plane with large 9-member rings (MRs) which are filled by lanthanide(III) ions into a {Ln[B5O9(OH)]}− 2D layer. Adjacent {Ln[B5O9(OH)]}− layers are bridged by remaining lanthanide (III) ions to form a 3D network of lanthanide borate. It is noteworthy that Ln2(CH3CO2)2[B5O9(OH)]·H2O (Ln = La 1; Ce 2; Pr 3) can be changed into Ln2(CH3CO2)2[B5O9(OH)] (Ln = La 4; Ce 5; Pr 6) under heating at 500 K. Compounds 1–4 display moderate SHG signals of about 2.0, 1.0, 1.4, and 2.5 times that of KH2PO4, respectively, and they are phase matchable. Their SHG responses mainly arise from the synergistic polarization effects of both asymmetric borate clusters and π-conjugated CH3COO– anions.
Co-reporter:Xue-Li Cao; Chun-Li Hu; Fang Kong
Inorganic Chemistry 2015 Volume 54(Issue 22) pp:10978-10984
Publication Date(Web):October 29, 2015
DOI:10.1021/acs.inorgchem.5b02074
Standard high-temperature solid-state reactions of NaCl, Nb2O5, and SeO2 resulted in two new sodium selenites containing a second-order Jahn–Teller (SOJT) distorted Nb5+ cation, namely, Na2Nb4O7(SeO3)4 (P1̅; 1) and NaNbO(SeO3)2 (Cmc21; 2). Compound 1 exhibits an unusual 3D [Nb4O7(SeO3)4]2– anionic network composed of 2D [Nb4O11(SeO3)2]6– layers which are further bridged by additional SeO32– anions via corner sharing; the 2D [Nb4O11(SeO3)2]6– layer is formed by unusual quadruple [Nb4O17]14– niobium oxide chains of corner-sharing NbO6 octahedra being further interconnected by selenite anions via Nb–O–Se bridges. The polar compound 2 features a 1D [NbO(SeO3)2]− anionic chain in which two neighboring Nb5+ cations are bridged by one oxo and two selenite anions. The alignments of the polarizations from the NbO6 octahedra in 2 led to a strong SHG response of ∼7.8 × KDP (∼360 × α-SiO2), which is the largest among all phases found in metal–Nb5+–Se4+/metal–Nb5+–Te4+–O systems. Furthermore, the material is also type I phase matchable. The above experimental results are consistent with those based on DFT theoretical calculations. Thermal stabilities and optical properties for both compounds are also reported.
Co-reporter:Jun-Ling Song, Xiang Xu, Chun-Li Hu, Fang Kong and Jiang-Gao Mao
CrystEngComm 2015 vol. 17(Issue 21) pp:3953-3960
Publication Date(Web):22 Apr 2015
DOI:10.1039/C5CE00509D
Three novel lead(II) borate–nitrates were obtained through a facile hydrothermal reaction by adjusting the concentrations of the starting materials, namely, [Pb6(μ4-O)4(BO3)](NO3) (1), H[Pb6(μ3-O)2(BO3)2](NO3)3 (2) and H[Pb8(μ4-O)3(μ3-O)(BO3)2](NO3)3 (3). All three compounds feature lead(II) oxo borate layers that are separated by nitrate anions. The 2D [Pb6(μ4-O)4(BO3)]+ layer parallel to the ab plane in 1 is built from 1D [Pb6(μ4-O)4]4+ chains along the a axis and bridging borate anions. The 2D H[Pb6(μ3-O)2(BO3)2]3+ layer in 2 which is perpendicular to the b axis is composed of “isolated” Pb2+ and tetranuclear [Pb4(μ3-O)2]4+ clusters interconnected by bridging BO3 groups. The [Pb8(μ4-O)3(μ3-O)(BO3)2]2+ (011) layer in 3 is composed of two types of lead(II) oxo chains, namely, 1D chains of [Pb4(μ4-O)2]4+ and 1D chains of [Pb4(μ4-O)(μ3-O)]4+, both elongated along the a axis, which are further interconnected by bridging borate anions. This study also demonstrates that a small change in the concentration of the starting materials could result in a product with a different density of the π-conjugated planar units.
Co-reporter:Xiang-Ying Qian, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2015 vol. 44(Issue 30) pp:13573-13580
Publication Date(Web):18 Jun 2015
DOI:10.1039/C5DT01370D
Three new octanuclear Th(IV) arsonates, namely [Th8(O)(L)6(HL)6(H2O)12]·19.5H2O (1) (H3L = o-HO3S–C6H4–AsO3H2), [Th8(O)(L)6(HL)6(H2O)10]·17H2O (2) and [Th8(O)(L)6(HL)6(H2O)5]·0.5H2O (3), with o-sulfophenylarsonic acid as the bridging ligand, have been prepared under hydrothermal conditions. Each complex contains [Th8O13]6+ octanuclear cluster cores composed of two [Th4O6]4+ units bridged by a μ2-oxo anion. The structure of compound 1 features a 0D highly symmetric polynuclear cluster encapsulating the octanuclear core of [Th8O13]6+ which is further decorated by six L3− and six HL2− ligands. Compound 2 features one-dimensional chains along the b-axis in which the neighboring clusters similar to 1 are bridged by a pair of sulfophenylarsonate ligands via M–O–S–O–M bridges. Compound 3 with chiral P212121 features two-dimensional cluster layers, in which each cluster connects with four neighbors via four M–O–S–O–M linkages. Compounds 2 and 3 display unusual broad green light emission bands at 523 nm (λex = 320 nm) and 517 nm (λex = 312 nm), respectively, which originate from the ligand-to-metal charge transfer (LMCT) transition.
Co-reporter:Xue-Li Cao, Fang Kong, Zhang-Zhen He and Jiang-Gao Mao
Dalton Transactions 2015 vol. 44(Issue 25) pp:11420-11428
Publication Date(Web):11 May 2015
DOI:10.1039/C5DT01257K
Three new transition metal copper(II) selenites or tellurites, namely, CdCu(SeO3)2 (1), HgCu(SeO3)2 (2), and Hg2Cu3(Te3O8)2 (3), have been obtained by conventional hydrothermal reactions of CdO (or Hg2Cl2), CuO and SeO2 (or TeO2). Compounds 1 and 2 are isostructural and crystallize in P21/c. Their structures feature a 3D anionic framework of Cu(SeO3)22− with 1D channels of eight-membered rings (MRs) along the c-axis and a-axis, respectively, which are filled by Cd2+ or Hg2+ cations. Compound 3 crystallizes in a tetragonal system of space group P4212. Its structure is characterized by a [Cu3(Te3O8)2]2− honeycomb layer composed of [Te3O8]4− anions interconnected by Cu2+ ions with 1D channels of 8-MRs along the c-axis. TOPOS analysis indicates that the copper(II) tellurite layer exhibits a new topological structure with a Schläfli symbol of {46·89}2{46}3. The above anionic copper(II) tellurite layers are further linked by dumbbell Hg22+ cations to form a novel 3D framework. Magnetic measurements based on magnetic susceptibility and heat capacity indicate that compounds 1 and 2 show a spin-singlet ground state with a spin gap based on the [Cu2O8]12− dimeric model, whereas compound 3 exhibits a 2D spin-system with an antiferromagnetic ordering around 25 K correlated with its honeycomb [Cu3(Te3O8)2]2− layer. Furthermore, crystalline structures, thermal stabilities, IR spectra and UV-Vis diffuse reflectance spectra have also been studied.
Co-reporter:Dr. Jun-Ling Song;Dr. Chun-Li Hu;Dr. Xiang Xu;Dr. Fang Kong ; Jiang-Gao Mao
Angewandte Chemie International Edition 2015 Volume 54( Issue 12) pp:3679-3682
Publication Date(Web):
DOI:10.1002/anie.201412344
Abstract
A new SHG material, namely, Pb2(BO3)(NO3), which contains parallel π-conjugated nitrate and borate anions, was obtained through a facile hydrothermal reaction by using Pb(NO3)2 and Mg(BO2)2⋅H2O as starting materials. Its structure contains honeycomb [Pb2(BO3)]∞ layers with noncoordination [NO3]− anions located at the interlayer space. Pb2(BO3)(NO3) shows a remarkable strong SHG response of approximately 9.0 times that of potassium dihydrogen phosphate (KDP) and the material is also phase-matchable. The large SHG coefficient of Pb2(BO3)(NO3) arises from the synergistic effect of the stereoactive lone pairs on Pb2+ cations and parallel alignment of π-conjugated BO3 and NO3 units. Based on its unique properties, Pb2(BO3)(NO3) may have great potential as a high performance NLO material in photonic applications.
Co-reporter:Dr. Jun-Ling Song;Dr. Chun-Li Hu;Dr. Xiang Xu;Dr. Fang Kong ; Jiang-Gao Mao
Angewandte Chemie 2015 Volume 127( Issue 12) pp:3750-3753
Publication Date(Web):
DOI:10.1002/ange.201412344
Abstract
A new SHG material, namely, Pb2(BO3)(NO3), which contains parallel π-conjugated nitrate and borate anions, was obtained through a facile hydrothermal reaction by using Pb(NO3)2 and Mg(BO2)2⋅H2O as starting materials. Its structure contains honeycomb [Pb2(BO3)]∞ layers with noncoordination [NO3]− anions located at the interlayer space. Pb2(BO3)(NO3) shows a remarkable strong SHG response of approximately 9.0 times that of potassium dihydrogen phosphate (KDP) and the material is also phase-matchable. The large SHG coefficient of Pb2(BO3)(NO3) arises from the synergistic effect of the stereoactive lone pairs on Pb2+ cations and parallel alignment of π-conjugated BO3 and NO3 units. Based on its unique properties, Pb2(BO3)(NO3) may have great potential as a high performance NLO material in photonic applications.
Co-reporter:Xiang Xu, Chun-Li Hu, Bing-Xuan Li, Bing-Ping Yang, and Jiang-Gao Mao
Chemistry of Materials 2014 Volume 26(Issue 10) pp:3219
Publication Date(Web):April 25, 2014
DOI:10.1021/cm500898q
Two new noncentrosymmetric isomeric silver polyiodates, namely, α-AgI3O8 (Pnc2) and β-AgI3O8 (I4̅), have been synthesized through the hydrothermal reactions of AgNO3 with I2O5. Both isomers exhibit layered structures that are constructed from I3O8– anions interconnected by Ag+ cations. The main structural difference between the two isomers lies in the different stacking fashions of [AgI3O8] layers along the c axis in order to meet the requirements of their space groups. Powder second-harmonic generation (SHG) measurements indicate that α-AgI3O8 and β-AgI3O8 are both phase-matchable materials with large SHG responses of approximately 9.0 and 8.0 times that of KH2PO4, respectively. UV–vis–NIR transmission spectra show that the cutoff absorption edges are 328 nm for α-AgI3O8 and 345 nm for β-AgI3O8. Thermal stability studies demonstrate that both isomers are thermally stable up to about 370 °C. Theoretical calculations based on DFT methods for the two AgI3O8 phases as well as the NaI3O8 analogue have been performed.
Co-reporter:Xue-Li Cao, Fang Kong, Chun-Li Hu, Xiang Xu, and Jiang-Gao Mao
Inorganic Chemistry 2014 Volume 53(Issue 16) pp:8816-8824
Publication Date(Web):August 7, 2014
DOI:10.1021/ic501548m
Hydrothermal reactions of PbCO3 (or PbCl2), V2O5, and SeO2 in KOH solution or HF solution resulted in three new lead(II)–vanadium(V) mixed-metal selenites, namely, Pb4V6O16(SeO3)3(H2O) (1), Pb2VO2(SeO3)2Cl (2), and PbVO2(SeO3)F (3). Compounds 1 and 2 are polar (space group P21), whereas compound 3 is centrosymmetric (space group Pbca). Compound 1 displays an unusual [V6O16(SeO3)3]8– anionic chain, which is composed by a 1D [V4O12]2– anionic chain that is further decorated by dimeric [V2O6(SeO3)3]8– units via corner-sharing. Compound 2 features two types of 1D chains, a cationic [Pb2Cl]3+ chain and a [VO2(SeO3)2]3– anionic chain, whereas compound 3 contains dimeric [V2O4(SeO3)2F2]2– units. The powder second-harmonic-generating (SHG) measurements indicate that compound 1 shows a weak SHG response of about 0.2 × KDP (KH2PO4) under 1400 nm laser radiation. Thermal stability and optical properties as well as theoretical calculations based on density functional theory methods were also performed.
Co-reporter:Chao Huang, Jian-Han Zhang, Chun-Li Hu, Xiang Xu, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry 2014 Volume 53(Issue 7) pp:3847-3853
Publication Date(Web):March 25, 2014
DOI:10.1021/ic5001842
Two new boroantimonates, namely, KSbB2O6 and BaSb2B4O12, have been successfully synthesized through high-temperature solid state reactions. Their structures feature two types of novel anionic 3D frameworks composed of 1D chains of corner-sharing SbO6 octahedra that are interconnected by B2O5 groups. The 1D chains of corner-sharing SbO6 octahedra in polar KSbB2O6 (space group Cc) are extended along the c-axis, whereas those in the centrosymmetric BaSb2B4O12 (space group C2/c) are propagated along the [101] direction. The K+ ions are located at the 1D tunnels of the anionic frameworks along both b- and c-axis, whereas Ba2+ ions are located at the 1D tunnels of the anionic frameworks along both the a- and c-axis. KSbB2O6 is a polar material that displays weak SHG response, whereas BaSb2B4O12 is centrosymmetric and not SHG active. Studies on their optical properties, thermal stability, and band structure calculations based on DFT methods have been also performed.
Co-reporter:Xiang Xu, Bing-Ping Yang, Chao Huang, and Jiang-Gao Mao
Inorganic Chemistry 2014 Volume 53(Issue 3) pp:1756-1763
Publication Date(Web):January 15, 2014
DOI:10.1021/ic4028942
Two new rubidium iodates, namely, β-RbIO3(HIO3)2 (1, P1) and Rb3(IO3)3(I2O5)(HIO3)4(H2O) (2, P21/c), have been synthesized by hydrothermal reaction and their structures determined by single-crystal X-ray diffraction. Compound 1 exhibits IO3– anions and neutral HIO3 molecules which are interconnected by Rb+ cations into three-dimensional structure. Compound 2 features a two-dimensional layered structure formed by IO3– anions and neutral HIO3 and dimeric I2O5 molecules interconnected by Rb+ cations. Large bulk crystal of 1 with dimensions of several millimeters has been grown. UV–vis–NIR transmission spectroscopy measurements on a slab of a polished crystal of 1 indicated that the crystal possesses a short-wavelength absorption edge onset at 305 nm. Powder second-harmonic generation (SHG) measurements on sieved crystals revealed that 1 is a type I phase-matchable material with an SHG response about 1.5 times that of KH2PO4. The Vickers hardness of crystal of 1 has been measured to be 110 HV, and the laser-induced damage threshold has been confirmed to be 18.26 J/cm2 with a laser wavelength of 1064 nm and a pulse duration of 10 ns. Moreover, thermal stabilities and vibrational spectra for both 1 and 2 have also been studied.
Co-reporter:Yu-Cheng Hao, Xiang Xu, Fang Kong, Jun-Ling Song and Jiang-Gao Mao
CrystEngComm 2014 vol. 16(Issue 33) pp:7689-7695
Publication Date(Web):12 Jun 2014
DOI:10.1039/C4CE00777H
Two new mixed metal borates, namely, PbCd2B6O12 and EuZnB5O10, have been synthesized successfully by high-temperature solid state reactions in platinum crucibles. Both compounds crystallize in the monoclinic space group P21/n. The structure of PbCd2B6O12 features a novel 3D framework of [Cd2B6O12]2− composed of [(B6O12)6−]n layers parallel to the ab plane, dimers of edge-sharing Cd(1)O7 octahedra and 1D chains of edge-sharing Cd(2)O6 octahedra, the Pb2+ ions are located at the voids of the structure. The [(B6O12)6−] layer exhibits 1D tunnels of 8-membered rings (MRs) which are filled by 1D chains of edge-sharing Cd(2)O6 octahedra, forming a novel 2D [CdB6O12]4− layer which is also parallel to the ab plane. Neighboring 2D [CdB6O12]4− layers are bridged by dimers of edge-sharing Cd(1)O7 polyhedra into a novel 3D [Cd2B6O12]2− anionic network. EuZnB5O10 is a new member in the LnMB5O10 (Ln = rare earth ion and M = divalent metal ion) family, its structure features a 3D network constructed of 2D [B5O10]5− layers that are crosslinked by Zn2O10 dimers composed of two edge-sharing ZnO6 octahedra, forming 1D tunnels of Zn4B4 8-membered rings (MRs) along the b-axis which are filled by the Eu3+ ions. The luminescent property measurements revealed that EuZnB5O10 emit strong red light at 610 nm with a 5D0 (Eu3+) lifetime of 1.0 ms and a quantum yield of about 18.4%.
Co-reporter:Xue-Li Cao, Chun-Li Hu, Xiang Xu, Fang Kong and Jiang-Gao Mao
Chemical Communications 2013 vol. 49(Issue 85) pp:9965-9967
Publication Date(Web):29 Aug 2013
DOI:10.1039/C3CC45747H
The replacement of NbO6 octahedra in Pb2NbO2(SeO3)2Cl by the TiO5F octahedra in Pb2TiOF(SeO3)2Cl induced a very large SHG enhancement from 2.3 × to 9.6 × KDP (KH2PO4), and both materials are type-I phase matchable. Theoretical calculations based on DFT methods indicate that the inclusion of F− anions in the d0-TM octahedral coordination unit has a great impact on the band structure and the SHG enhancement of the material.
Co-reporter:Bing-Ping Yang, Chun-Li Hu, Xiang Xu, Chao Huang, and Jiang-Gao Mao
Inorganic Chemistry 2013 Volume 52(Issue 9) pp:5378-5384
Publication Date(Web):April 5, 2013
DOI:10.1021/ic4003324
The synthesis, crystal and electronic structures, and optical properties of the first zinc(II) vanadium(V) iodate, namely, Zn2(VO4)(IO3), are reported. Zn2(VO4)(IO3) crystallizes in the noncentrosymmetric (NCS) and polar space group Pc (No. 7) with a = 5.2714(8) Å, b = 10.0402(11) Å, c = 5.5070(8) Å, β = 101.326(10)°, and Z = 2. It displays a novel three-dimensional (3D) network structure composed of ZnO5, ZnO6, VO4, and IO3 polyhedra. One-dimensional (1D) chains of edge-sharing ZnO5 polyhedra and 1D chains of corner-sharing ZnO6 octahedra along the c-axis are interconnected via corner-sharing into a two-dimensional (2D) zinc oxide layer, and such layers are bridged by both VO4 tetrahedra and IO3 groups into a 3D network. The polarity in the structure is imparted by the alignment of the stereochemically active lone pairs of the iodate anions along the c-axis. The second harmonics generation (SHG) measurements on powder samples of Zn2(VO4)(IO3) under 1064-nm laser radiation revealed a large response of ∼6 × KDP, which is Type I phase-matchable. Thermal stability and optical properties, as well as theoretical calculations based on DFT methods, were also performed.
Co-reporter:Xiang Xu, Chun-Li Hu, Fang Kong, Jian-Han Zhang, Jiang-Gao Mao, and Junliang Sun
Inorganic Chemistry 2013 Volume 52(Issue 10) pp:5831-5837
Publication Date(Web):May 6, 2013
DOI:10.1021/ic302774h
A new alkali-metal borogermanate with noncentrosymmetric structure, namely, Cs2GeB4O9, has been discovered, and a large crystal with dimensions of 20 × 16 × 8 mm3 has been grown by a high-temperature top-seeded solution method using Cs2O–B2O3 as a flux. The compound crystallizes in the tetragonal space group I4̅ with a = b = 6.8063(2) Å, c = 9.9523(7) Å, V = 461.05(4) Å3, and Z = 2. It features a three-dimensional anionic open framework based on GeO4 tetrahedra and B4O9 clusters that are interconnected via corner-sharing, forming one-dimensional channels of nine-/ten-membered rings along the a and b axes, which are occupied by Cs+ cations. Cs2GeB4O9 exhibits a very high thermal stability with a melting point of 849 °C, and it possesses a short-wavelength absorption edge onset at 198 nm determined by UV–vis transmission spectroscopy measurements on a slab of polished crystal. Powder second-harmonic generation (SHG) measurement on sieved crystals reveals that Cs2GeB4O9 is a type I phase-matchable material with a strong SHG response of about 2.8 × KH2PO4. The preliminary investigation indicates that Cs2GeB4O9 is a new promising second-order nonlinear-optical crystalline material.
Co-reporter:Jun-Ling Song, Chun-Li Hu, Xiang Xu, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry 2013 Volume 52(Issue 15) pp:8979-8986
Publication Date(Web):July 8, 2013
DOI:10.1021/ic401175r
Using lead metaborate as starting material, by only adjusting pH values of the reaction systems, a series of lead(II) borates were obtained in high yields. The new polar material, namely, Pb2B3O5.5(OH)2 (1), crystallizes in the noncentrosymmetric space group Pnn2 of the orthorhombic system. Its structure features a novel three-dimensional (3D) anionic network with large 14 member rings (MRs) tunnels composed of unique one-dimensional (1D) chains and dimeric B2O7 fragments, both of which are built up from solely BO4 tetrahedra, and the Pb2+ cations are located at the above 14-MRs tunnels. The synergistic effect of the stereoactive lone-pairs on Pb2+ cations in 1 produces a strong SHG response of ∼3× KDP (KH2PO4) which is type I phase-matchable. The first example of lead(II) borate nitrate, namely, [Pb3(B3O7)](NO3) (2), crystallizes in space group Pnma, and its structures features a 3D lead(II) borate cationic network structure in which (B3O7)5– anions are bridged by lead(II) cations, the nitrate anions are isolated, and located at the small voids of the cationic network. Thermal stability and optical properties as well as theoretical calculations based on density functional theory (DFT) methods were also performed.
Co-reporter:Chao Huang, Chun-Li Hu, Xiang Xu, Bing-Ping Yang, and Jiang-Gao Mao
Inorganic Chemistry 2013 Volume 52(Issue 19) pp:11551-11562
Publication Date(Web):September 16, 2013
DOI:10.1021/ic401891f
The syntheses, crystal structures, and characterizations of a series of monovalent metal gold(III) iodates, namely, α-NaAu(IO3)4, β-NaAu(IO3)4, RbAu(IO3)4, α-CsAu(IO3)4, β-CsAu(IO3)4, and AgAu(IO3)4 are reported. Their structures feature Au(IO3)4– anions that are separated by alkali metal ions or silver(I) ions. The Au(IO3)4– anions in the polar α-NaAu(IO3)4, RbAu(IO3)4, and α-CsAu(IO3)4 are polar with all four iodate groups being located only above (or below) the AuO4 square plane (cis- configuration). α-NaAu(IO3)4, RbAu(IO3)4, and α-CsAu(IO3)4 display moderate strong Second-Hamonic Generation (SHG) responses of 1.17 ×, 1.33 ×, and 1.17 × KTP (KTiOPO4), respectively, and all three materials are type-I phase-matchable. The Au(IO3)4– anions in centrysymmetric β-NaAu(IO3)4, β-CsAu(IO3)4, and AgAu(IO3)4 are nonpolar with the four iodate groups of the Au(IO3)4– anion being located both above and below the AuO4 square plane (trans- configuration). IR and UV spectra, luminescent and ferroelectric properties have also been measured. Theoretical calculations of their optical properties based on density functional theory (DFT) methods were performed by using the CASTEP total-energy code.
Co-reporter:Yu-Cheng Hao ; Chun-Li Hu ; Xiang Xu ; Fang Kong
Inorganic Chemistry 2013 Volume 52(Issue 23) pp:13644-13650
Publication Date(Web):November 14, 2013
DOI:10.1021/ic402214p
Two new alkaline-earth strontium borogermanates, namely, SrGe2B2O8 and Sr3Ge2B6O16, have been successfully synthesized through high-temperature solid state reactions. They represent the first examples of strontium borogermanates. SrGe2B2O8 crystallized in space group Pnma, and its structure features a novel three-dimensional [Ge2B2O8]2– framework composed of alternative linkages of the B2O7 and Ge2O7 dimeric units with one-dimensional (1D) tunnels of eight-membered rings (MRs) along the b axis that are filled by the Sr2+ cations. Sr3Ge2B6O16 is isostructural with Ba3Ge2B6O16 and crystallizes in centrosymmetric space group P1̅. Its structure features a two-dimensional layer that is composed of circular B6O16 clusters and GeO4 tetrahedra that are interconnected via corner sharing, forming 1D four- and six-MR tunnels along a axis. Sr(1) cations are located in the six-MR tunnels, whereas Sr(2) cations are located in the interlayer space. Studies of their optical properties and thermal stability as well as band structure calculations based on density functional theory methods have been also performed.
Co-reporter:Xiang-Ying Qian, Jun-Ling Song, and Jiang-Gao Mao
Inorganic Chemistry 2013 Volume 52(Issue 4) pp:1843-1853
Publication Date(Web):February 6, 2013
DOI:10.1021/ic301935g
Four new layered silver(I) organoarsonates, namely, [Ag3(L3)(CN)] (1) (H2L3 = (PhAsO2H)2O), [Ag3(L4)(CN)] (2) (H2L4 = (2-NO2-C6H4-AsO2H)2O), [Ag3(HL5)(H2L5)] (3) (H3L5 = 3-NO2-4-OH-C6H3-AsO3H2) and [Ag2(HL5)] (4), were synthesized under solvothermal conditions. During the preparations of 1 and 2, condensation of organoarsonate ligands (H2L1 = Ph-AsO3H2; H2L2 = 2-NO2-C6H4-AsO3H2) and the decomposition of acetonitrile molecules to cyanide anions occurred. Single crystals of H2L4 ligand and compounds 1–4 were isolated, and their crystal structures have been determined by single crystal X-ray diffraction studies. In 1, the one-dimensional (1D) chains based on Ag(I) ions and {L3}2– anions are further interconnected by CN– into two-dimensional (2D) layers. In 2, adjacent Ag(I) ions within the silver(I) organoarsonate layer are further bridged by μ4-CN– anions with very short Ag···Ag contacts. In 3, the hexanuclear {Ag6O12} clusters are interconnected by bridging organoarsonate ligands into a silver(I) arsonate hybrid layer. In 4, the right-handed {Ag4O4} chains are further interconnected by organoarsonate ligands as well as additional Ag–O–Ag bridges into a novel silver(I) arsonate layer. Compounds 1 and 2 display red and orange-red emissions, respectively, which may be assigned to be an admixture of ligand-to-metal charge transfer (LMCT) and metal-centered (4d-5s/5p) transitions perturbed by Ag(I)···Ag(I) interactions. Upon cooling from room temperature to 10 K, compound 1 exhibits interesting temperature-dependent emissions.
Co-reporter:Xiang Xu, Chun-Li Hu, Bing-Ping Yang and Jiang-Gao Mao
CrystEngComm 2013 vol. 15(Issue 38) pp:7776-7782
Publication Date(Web):31 Jul 2013
DOI:10.1039/C3CE41185K
Systematic explorations of new compounds in the unexplored Ag+–Mn2+/Mn3+–iodate system led to three new silver Mn2+ (or Mn3+)-mixed metal iodates, namely, AgMn(IO3)3, AgMn(IO3)4 and Ag3Mn(IO3)6. These compounds feature the same building units of MnO6 octahedron and IO3, but the different coordination modes of the iodate groups in these compounds led to three different types of anionic structures ranging from a zero-dimensional (0D) cluster to a two-dimensional (2D) layer. Interestingly, the dimensions of the anionic structure decrease with an increase in the IO3/Mn molar ratio in the formula. AgMn(IO3)3 exhibits a 2D [Mn2(IO3)6]n2n− anionic layer in which the Mn2O2 rings are further decorated by terminal iodates and interconnected by bidentate and tridentate bridging iodate groups. AgMn(IO3)4 displays a one-dimensional (1D) [Mn(IO3)4]nn− anionic chain in which each pair of MnO6 octahedra is bridged by a pair of IO3 groups, and within the chain each manganese center is also attached with two terminal iodate groups from both sides of the chain. Ag3Mn(IO3)6 features isolated 0D [Mn(IO3)6]3− anions. The Ag+ cations in all three compounds act as spacers between these anions. Optical, thermal stability and magnetic susceptibility measurements for AgMn(IO3)3 and AgMn(IO3)4 have also been performed.
Co-reporter:Tian-Hua Zhou, Zhang-Zhen He, Xiang Xu, Xiang-Ying Qian, and Jiang-Gao Mao
Crystal Growth & Design 2013 Volume 13(Issue 2) pp:838-843
Publication Date(Web):December 12, 2012
DOI:10.1021/cg301542n
The hydrothermal reactions of 4-[(phosphonomethylamino)methyl]benzoic acid (H3L) with M(NO3)2 (M = Co, Zn) afford two metal phosphonates, namely, Co(HL) and Zn(HL). Both of them display a 3D polar pillared layered structure. Magnetic measurements confirm that Co(HL) exhibits a canted antiferromagnetic ordering at about 2 K. A weak ferromagnetic component at low temperature is attributed to the Dzyaloshinskii–Moriya (DM) interactions arising from the polar noncentrosymmetric crystal structure. The ZnII compound exhibits a second harmonic generation (SHG) response of approximately 0.2 times that of potassium dihydrogen phosphate (KDP).
Co-reporter:Bing-Ping Yang, Xiang Xu, Chao Huang and Jiang-Gao Mao
CrystEngComm 2013 vol. 15(Issue 48) pp:10464-10469
Publication Date(Web):04 Nov 2013
DOI:10.1039/C3CE41653D
Systematic explorations of new compounds in the divalent transition metal–vanadium(V)–iodate system by hydrothermal reactions led to three quinary mixed metal iodates, namely, K4TM4(V2O7)2(IO3)4(H2O) (TM = Zn, Ni, Co). They represent the first examples of quinary mixed metal vanadium iodates. The structures of K4TM4(V2O7)2(IO3)4(H2O) (TM = Zn, Ni, Co) are quite unusual and consist of sandwich-like double layers of 1∞[TM4(V2O7)2(IO3)4(H2O)]4− that are separated by K+ cations. The interconnection of TMO6 units via tridentate bridging IO3− groups resulted in a 2D sheet parallel to the ab-plane. Two such sheets are bridged by V2O7 units into a unique sandwich-like double layer. V2O7 units are observed in iodates for the first time. Thermal stability and optical properties as well as magnetic properties for the Co and Ni phases were studied.
Co-reporter:Jun-Hui Liu, Fang Kong, Yan-Li Gai, Jiang-Gao Mao
Journal of Solid State Chemistry 2013 Volume 197() pp:228-235
Publication Date(Web):January 2013
DOI:10.1016/j.jssc.2012.08.019
Two new bismuth arsenites with two different structural types, namely, Bi2O(AsO3)Cl (1), Bi8O6(AsO3)2(AsO4)2 (2), have been synthesized by the solid-state reactions. Compound 1 exhibits novel 2D bismuth arsenite layers with Bi4O4 rings capped by oxide anions, which are further interconnected by Bi–Cl–Bi bridges into a 3D network. Compound 2 contains both arsenite and arsenate anions, its 3D structures are based on 1D bismuth arsenite and 1D bismuth arsenate chains both along b-axis, which are interconnected by oxide anions via Bi–O–Bi bridges, forming 1D tunnels of Bi4As4 8-membered rings (MRs) along b-axis, the lone pairs of the arsenite groups are orientated toward the centers of the above tunnels. Thermogravimetric analysis indicated that both compounds display high thermal stability. Optical property measurements revealed that they are wide band-gap semiconductors. Both compounds display broad green-light emission bands centered at 506 nm under excitation at 380 and 388 nm.Graphical abstractSolid state reactions of Bi2O3 (BiCl3) and As2O3 yielded two new compounds with two different structural types, namely, Bi2O(AsO3)Cl (1), Bi8O6(AsO3)2(AsO4)2 (2). They represent the first examples of bismuth arsenates.Highlights► Solid state reactions of Bi2O3 (BiCl3) and As2O3 yielded two new phases. ► They represent the first examples of bismuth arsenites. ► The two compounds exhibit two different structural types.
Co-reporter:Chuan-Fu Sun, Chun-Li Hu and Jiang-Gao Mao
Chemical Communications 2012 vol. 48(Issue 35) pp:4220-4222
Publication Date(Web):05 Mar 2012
DOI:10.1039/C2CC30326D
A new polar material containing two types of stereoactive lone-pairs has been synthesized. The unique parallel alignment of the stereoactive lone-pairs on Pb2+ cations and the synergistic effect of two types of stereoactive lone-pairs on I5+ and Pb2+ cations make it exhibit a very large second-harmonic generation response of about 8 × KDP (KH2PO4).
Co-reporter:Ting Hu, Chun-Li Hu, Fang Kong, Jiang-Gao Mao, and Thomas C. W. Mak
Inorganic Chemistry 2012 Volume 51(Issue 16) pp:8810-8817
Publication Date(Web):July 31, 2012
DOI:10.1021/ic3006376
Three new galloborates, namely, GaB5O8(OH)2(en)2·H2O (1), LiGa(OH)(BO3)(H2O) (2), and Rb2Ga(B5O10)(H2O)4 (3), have been synthesized by hydrothermal reactions. Compound 1 is the first example of a galloborate that contains an organic component. It crystallizes in space group P21/c, and its crystal structure exhibits an infinite zigzag chain consisting of [B5O8(OH)2]3– anions and GaO2N4 octahedra interconnected via corner sharing. Compound 2 crystallizes in space group P31c with a layered structure composed of GaO4, LiO4, and BO3 building units. Compound 3 belongs to chiral space group C2221; the basic building blocks of the structure are the [B5O10]5– cluster anion and GaO4 tetrahedron, which are interconnected to form a three-dimensional network with tunnels of Ga2B6 eight-membered rings (8-MRs) which are filled by Rb+ cations and lattice water molecules. Interestingly, Rb2Ga(B5O10)(H2O)4 displays a moderate second-harmonic generation (SHG) response comparable to that of KH2PO4 (KDP), and it is phase matchable. Band structure and optical property calculations for Rb2Ga(B5O10)(H2O)4 based on DFT methods were also performed.
Co-reporter:Jian-Han Zhang, Fang Kong, Bing-Ping Yang and Jiang-Gao Mao
CrystEngComm 2012 vol. 14(Issue 24) pp:8727-8733
Publication Date(Web):18 Oct 2012
DOI:10.1039/C2CE26524A
The first four metal boroselenites, namely, K2Se3B2O10, ASeB3O7 (A = Na, K), and Li2SeB8O15, have been synthesized by high temperature solid state reactions. Interestingly, the different cationic sizes and their coordination geometries led to three different types of anionic boroselenite frameworks ranging from a one-dimensional (1D) chain, to two-dimensional (2D) layers to a three-dimensional (3D) network. K2Se2B2O10 features a novel 1D [Se3B2O10]2− chain based on isolated B2O7 and SeO3 groups. ASeB3O7 (A = Na, K) feature a layered [SeB3O7]− architecture built of 1D corner-sharing B3O7 clusters that are further bridged by Se atoms. Li2SeB8O15 features an interesting 3D [SeB8O15]2− anionic framework composed of B3O7 groups and SeO3 units. Such 3D frameworks are further interpenetrated with each other into a 2-fold interpenetrating structure.
Co-reporter:Su-Yun Zhang, Chun-Li Hu, Pei-Xin Li, Hai-Long Jiang and Jiang-Gao Mao
Dalton Transactions 2012 vol. 41(Issue 31) pp:9532-9542
Publication Date(Web):11 Jun 2012
DOI:10.1039/C2DT30560G
Four new lead(II) or bismuth(III) selenites and a tellurite, namely, Pb3(TeO3)Cl4, Pb3(SeO3)2Br2, Pb2Cd3(SeO3)4I2(H2O), Pb2Ge(SeO3)4 and BiFe(SeO3)3, have been prepared and structurally characterized by single crystal X-ray diffraction (XRD) analyses. These compounds exhibit five different types of structures. The structure of Pb3(TeO3)Cl4 features a three-dimensional (3D) lead(II) chloride network with tellurite anions filling in the 1D tunnels of Pb4 4-member rings (MRs) along the c-axis. Pb3(SeO3)2Br2 contains a 3D network composed of lead(II) selenite layers interconnected by bromide anions. Pb2Cd3(SeO3)4I2(H2O) is a 3D structure based on 2D cadmium(II) selenite layers which are further connected by 1D lead(II) iodide ladder chains with lattice water molecules located at the 1D tunnels of the structure. Pb2Ge(SeO3)4 features a 3D framework constructed by the alternate arrangement of lead(II) selenite layers and germanium(IV) selenite layers in the [100] direction. The structure of BiFe(SeO3)3 is built on the 3D anionic framework of ion(III) selenite with the bismuth(III) ions located at its Fe6Se6 12-MR tunnels. Pb3(TeO3)Cl4 (Pna21) is polar and BiFe(SeO3)3 (P212121) is noncentrosymmetric. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation indicate that BiFe(SeO3)3 exhibits a weak SHG efficiency of about 0.2 × KH2PO4 (KDP). Magnetic property measurements for BiFe(SeO3)3 show a dominant antiferromagnetic interaction with weak spin-canting at low temperatures. IR, UV-vis and thermogravimetric, as well as electronic structure calculations were also performed.
Co-reporter:Fang Kong, Chun-Li Hu, Xiang Xu, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2012 vol. 41(Issue 18) pp:5687-5695
Publication Date(Web):22 Feb 2012
DOI:10.1039/C2DT12437H
Four new quaternary molybdenum selenites, namely, HRb3(Mo5O15)(SeO3)2(H2O)21, α-Rb4Mo5O15(SeO3)2(H2O)22, β-Rb4Mo5O15(SeO3)2(H2O)23 and K4Mo5O15(SeO3)2(H2O)24 were synthesized by hydrothermal reactions. All of the four compounds feature a zero-dimensional (0D) [(Mo5O15)(SeO3)2]4− anionic unit composed of a five-member MoO6 octahedral ring capped by two SeO32− trigonal pyramids, with the Rb+/K+ or/and H+ cations and water molecules acting as spacers and keeping charge balance. Although these compounds exhibit similar chemical formula, their structures are slightly different. HRb3(Mo5O15)(SeO3)2(H2O)21 crystallizes in a polar space group (Pca21). α-Rb4Mo5O15(SeO3)2(H2O)22 crystallizes in a centrosymmetric (CS) space group (P21/n) whereas β-Rb4Mo5O15(SeO3)2(H2O)23 and K4Mo5O15(SeO3)2(H2O)24 are isomorphous, crystallize in a chiral space group (C2). The chiral structures of 3 and 4 contain two similar polyanions of [Mo5O15(SeO3)2]4− with opposite handedness. Second-harmonic-generation (SHG) measurements indicate that 1, 3 and 4 are all SHG-active. Compound 1 displays a weak SHG response of about 20% of that of KDP (KH2PO4) and is phase-matchable whereas the SHG responses of 3 and 4 are very weak (less than 5% of that of KDP). Thermal analyses and optical property measurements have also been performed.
Co-reporter:Xiang-Ying Qian, Jian-Han Zhang, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2012 vol. 41(Issue 4) pp:1229-1236
Publication Date(Web):28 Nov 2011
DOI:10.1039/C1DT11481F
The first examples of lanthanide(III) organoarsonates, Ln(L1)(H2O)3 (Ln = La (1), H3L1 = 4-hydroxy-3-nitrophenylarsonic acid), Ln(L1)(H2O)2 (Ln = Nd (2), Gd (3)), and mixed-ligand lanthanide(III) organoarsonates, Ln2(HL1)2(C2O4)(H2O)2 (Ln = Nd (4), Sm (5), Eu (6)), were hydrothermally synthesized and structurally characterized. Compounds 1–3 feature a corrugated lanthanide arsonate layer, in which 1D lanthanide arsonate inorganic chains are further interconnected via bridging L13− ligands. Compounds 4–6 exhibit a complicated 3D network. The interconnection of the lanthanide(III) ions by the bridging arsonate ligand leads to the formation of a novel 3D framework with long narrow 1D tunnels along the a-axis, with the oxalate anions are located at the above tunnels and bridging with lanthanide(III) ions. Compounds 2 and 4 exhibit the characteristic emission bands of the Nd(III) ion, whereas compound 6 displays the characteristic emission bands of the Eu(III) ion. The magnetic properties of compounds 3–6 were also investigated.
Co-reporter:Jun-Hui Liu, Zhang-Zhen He, Fang Kong, Xiang Xu, Chuan-Fu Sun, Jiang-Gao Mao
Journal of Solid State Chemistry 2012 Volume 192() pp:263-272
Publication Date(Web):August 2012
DOI:10.1016/j.jssc.2012.04.022
Systematic explorations in vanadium arsenites and arsenates led to the isolation four new compounds, namely, α-(VIVO)3(AsIIIO3)2 (1), β-(VIVO)3(AsIIIO3)2 (2), (VIVO)[VIVO(H2O)]2(AsVO4)2 (3), VIIIVIVO2(AsVO4) (4). Compounds 1, 2 and 4 were synthesized by standard solid-state reactions, and compound 3 is a vanadium arsenate dihydrate synthesized through hydrothermal reactions. Compounds 1 and 2 are isomers, and they represent the first examples of ternary inorganic vanadium(IV) arsenites. Single crystal X-ray diffraction analysis indicated that the four compounds display four different structural types. Magnetic property measurements for compound 1 indicated that it exhibits ferromagnetism with the Curie temperature Tc=65 K. Thermal stability and optical properties for compounds 1 and 3 were also investigated.Graphical abstractHydrothermal or solid state reactions of V2O5 (or VO2) and As2O3 yielded four new ternary compounds with four different types of structures, namely, α-(VO)3(AsO3)2 (1), β-(VO)3(AsO3)2 (2), (VO)[VO(H2O)]2(AsO4)2 (3), (VO)2(AsO4) (4). α-(VO)3(AsO3)2 (1), β-(VO)3(AsO3)2 (2) represent the first examples of ternary inorganic vanadium(IV) arsenites.Highlights► Hydrothermal or solid state reactions of V2O5 (or VO2) and As2O3 yielded two new arsenites. ► They represent the first examples of ternary vanadium arsenites. ► Two new ternary vanadium arsenates were also obtained. ► They exhibit four different structural types.
Co-reporter:Jian-Han Zhang, Fang Kong, Xiang Xu, Jiang-Gao Mao
Journal of Solid State Chemistry 2012 Volume 195() pp:63-72
Publication Date(Web):November 2012
DOI:10.1016/j.jssc.2011.12.045
Borogermanates are a class of very important compounds in materials chemistry. In this paper, the syntheses, structures, and properties of metal borogermanates are reviewed. Organically templated borogermanates with zeolite-like open-frameworks show potential applications as microporous materials. Many compounds in alkali or alkaline-earth borogermanate systems are structurally acentric or polar, some of which exhibit excellent Second Harmonic Generation (SHG) coefficients, wide transparency regions, and high optical-damage thresholds as well as excellent thermal stability. Most of the lanthanide borogermanates are structurally centrosymmetric and not SHG active; however, they are able to emit strong luminescence in visible or near-IR region. In the B-rich compounds, BO3 and BO4 groups can be polymerized into a variety of discrete polynuclear anionic cluster units or extended architectures via B–O–B bridges; whereas in the Ge-rich compounds, GeO4 and GeO6 polyhedra can also be polymerized. The combinations of borate and germinate afforded rich structural and topological types.Graphical abstractBorogermanates are a class of very important compounds in materials chemistry. Both BOx (x=3, 4) and GeOy (y=4, 6) polyhedra can be polymerized into a variety of discrete polynuclear anionic cluster units or extended architectures. The combinations of borate and germanate groups in the same oxide framework not only give rise to a rich structural chemistry, but also afford many polar compounds with good SHG properties.Highlights► Borogermanates are a class of new materials. ► They feature to be the combination of B and Ge atoms into the same oxide framework. ► They can form a large number of novel 2D and 3D framework structures. ► Some of them are acentric or polar with moderate strong SHG responses.
Co-reporter:Chuan-Fu Sun ; Chun-Li Hu ; Xiang Xu ; Bing-Ping Yang
Journal of the American Chemical Society 2011 Volume 133(Issue 14) pp:5561-5572
Publication Date(Web):March 23, 2011
DOI:10.1021/ja200257a
Four new potassium vanadyl iodates based on lone-pair-containing IO3 and second-order Jahn−Teller distorted VO5 or VO6 asymmetric units, namely, α-KVO2(IO3)2(H2O) (Pbca), β-KVO2(IO3)2(H2O) (P212121), K4[(VO)(IO3)5]2(HIO3)(H2O)2·H2O (P1), and K(VO)2O2(IO3)3 (Ima2) have been successfully synthesized by hydrothermal reactions. α-KVO2(IO3)2(H2O) and β-KVO2(IO3)2(H2O) exhibit two different types of 1D [VO2(IO3)2]− anionic chains. Neighboring VO6 octahedra in the α-phase are corner-sharing into a 1D chain with the IO3 groups attached on both sides of the chain in a uni- or bidentate bridging fashion, whereas those of VO5 polyhedra in the β-phase are bridged by IO3 groups into a right-handed helical chain with remaining IO3 groups being grafted unidentately on both sides of the helical chain. The structure of K4[(VO)(IO3)5]2(HIO3)(H2O)2·H2O contains novel isolated [(VO)(IO3)5]2− units composed of one VO6 octahedron linked to five IO3 groups and one terminal O2− anion. The structure of K(VO)2O2(IO3)3 exhibits a 1D [(VO)2O2(IO3)3]− chain in which neighboring VO6 octahedra are interconnected by both oxo and bridging iodate anions. Most interestingly, three of four compounds are noncentrosymmetric (NCS), and K(VO)2O2(IO3)3 displays a very strong second-harmonic generation response of about 3.6 × KTP, which is phase matchable. It also has high thermal stability, a wide transparent region and moderate hardness as well as an excellent growth habit. Thermal analyses and optical and ferroelectric properties as well as theoretical calculations have also been performed.
Co-reporter:Tian-Hua Zhou, Jian Zhang, Hai-Xia Zhang, Rui Feng and Jiang-Gao Mao
Chemical Communications 2011 vol. 47(Issue 31) pp:8862-8864
Publication Date(Web):11 Jul 2011
DOI:10.1039/C1CC12914G
An unusual ligand-conformation driving chiral generation and symmetry-breaking crystallization occurred simultaneously in the formation of a layered zinc(II) arsonate Zn(Hcapa)(4,4′-bipy) (1P) and its enantiomorph (1M) without any chiral sources, indicating that the asymmetrical crystallization of the coordination polymer from achiral precursors may be induced by the conformation control of the ligand.
Co-reporter:Jian-Han Zhang ; Chun-Li Hu ; Xiang Xu ; Fang Kong
Inorganic Chemistry 2011 Volume 50(Issue 5) pp:1973-1982
Publication Date(Web):January 13, 2011
DOI:10.1021/ic102451n
Three novel rubidium borogermanates with three types of noncentrosymmetric structures, namely, RbGeB3O7, Rb2GeB4O9, and Rb4Ge3B6O17, have been synthesized by high-temperature solid-state reactions in platinum crucibles. The structure of RbGeB3O7 features a three-dimensional (3D) anionic framework composed of cyclic B3O7 groups corner-sharing GeO4 tetrahedra. The structure of Rb2GeB4O9 shows a 3D anionic framework based on B4O9 clusters connected by GeO4 tetrahedra via corner sharing. The structure of Rb4Ge3B6O17 is a novel 3D anionic framework composed of cyclic B3O8 groups, Ge2O7 dimers, and GeO4 tetrahedra that are interconnected via corner sharing. Second harmonic generation (SHG) measurements indicate that RbGeB3O7, Rb2GeB4O9, and Rb4Ge3B6O17 display moderate SHG responses that are approximately 1.3, 2.0, and 1.3 × KH2PO4 (KDP), respectively, which are slightly smaller than those from theoretical calculations (about 3.7, 2.8, and 2.4 × KDP, respectively).
Co-reporter:Jian-Han Zhang, Fang Kong, and Jiang-Gao Mao
Inorganic Chemistry 2011 Volume 50(Issue 7) pp:3037-3043
Publication Date(Web):March 9, 2011
DOI:10.1021/ic1025697
Two new barium borogermanates with two types of novel structures, namely, Ba3[Ge2B7O16(OH)2](OH)(H2O) and Ba3Ge2B6O16, have been synthesized by hydrothermal or high-temperature solid-state reactions. They represent the first examples of alkaline-earth borogermanates. Ba3[Ge2B7O16(OH)2](OH)(H2O) crystallized in a polar space group Cc. Its structure features a novel three-dimensional anionic framework composed of [B7O16(OH)2]13− polyanions that are bridged by Ge atoms with one-dimensional (1D) 10-membered-ring (MR) tunnels along the b axis. The BaII cations, hydroxide ions, and water molecules are located at the above tunnels. Ba3Ge2B6O16 crystallizes in centrosymmetric space group P1̅. Its structure exhibits a thick layer composed of circular B6O16 units connected by GeO4 tetrahedra via corner sharing, forming 1D 4- and 6-MR tunnels along the c axis. Ba1 ions reside in the tunnels of the 6-MRs, whereas Ba2 ions are located at the interlayer space. Both compounds feature new types of topological structures. Second-harmonic-generation (SHG) measurements indicate that Ba3[Ge2B7O16(OH)2](OH)(H2O) displays a weak SHG response of about 0.3 times that of KH2PO4. Optical, thermal stability, and ferroelectric properties as well as theoretical calculations have also been performed.
Co-reporter:Xiang Xu, Chun-Li Hu, Fan Kong, Jian-Han Zhang, and Jiang-Gao Mao
Inorganic Chemistry 2011 Volume 50(Issue 18) pp:8861-8868
Publication Date(Web):August 17, 2011
DOI:10.1021/ic2008254
Two new acentric borogermanates, Ca10Ge16B6O51 (Pba2) and Cd12Ge17B8O58 (P4̅), have been successfully synthesized by high-temperature solid-state reactions of CaCO3 (or CdCO3), GeO2, and H3BO3. Both structures display the same one-dimensional (1D) [Ge4O12]n chains composed of GeO4 tetrahedra and GeO6 octahedra. In Ca10Ge16B6O51, neighboring 1D [Ge4O12]n chains are condensed into a two-dimensional (2D) [Ge4O10.75]n layer via corner sharing, and such layers are further interconnected by “isolated” BO4 tetrahedra and B2O7 dimers into a three-dimensional (3D) framework, forming 1D tunnels of 5-, 6-, and 7-MRs along the c axis that are occupied by Ca2+ cations. In Cd12Ge17B8O58, neighboring 1D [Ge4O12]n chains are interconnected into a [Ge4O10.5]n open framework via corner sharing with large pores filled by big [Ge(B2O7)4]28– clusters, leading to formation of three types of 1D tunnels of 5-, 6-, and 7-membered rings (MRs) along the c axis which are occupied by the Cd2+ cations. Both compounds are transparent in the range of 0.3–6.67 μm and exhibit very weak SHG responses.
Co-reporter:Su-Yun Zhang
Inorganic Chemistry 2011 Volume 50(Issue 11) pp:4934-4943
Publication Date(Web):April 28, 2011
DOI:10.1021/ic200149y
Hydrothermal reactions of lanthanide(III) oxide, molybdenum oxide, and SeO2 at 230 °C lead to five new molybdenum-rich quaternary lanthanide selenites with two types of structures, namely, H3Ln4Mo9.5O32(SeO3)4(H2O)2 (Ln = La, 1; Nd, 2) and Ln2Mo3O10(SeO3)2(H2O) (Ln = Eu, 3; Dy, 4; Er, 5). Compounds 1 and 2 feature a complicated three-dimensional (3D) architecture constructed by the intergrowth of infinite molybdenum selenite chains of [Mo4.75SeO19]5.5– and one-dimensional (1D) lanthanide selenite chains. The structures of 3, 4, and 5 exhibit 3D network composed of 1D [Mo3SeO13]4– anionic chains connected by lanthanide selenite chains. The molybdenum selenite chain of [Mo4.75SeO19]5.5– in 1 and 2 is composed of a pair of [Mo3SeO13]4– chains as in 3, 4, and 5 interconnected by a [Mo1.75O8]5.5– double-strand polymer via corner-sharing. The lanthanide selenite chains in both structures are similar in terms of coordination modes of selenite groups as well as the coordination environments of lanthanide(III) ions. Luminescent studies at both room temperature and 10 K indicate that compound 2 displays strong luminescence in the near-IR region and compound 3 exhibits red fluorescent emission bands with a luminescent lifetime of 0.57 ms. Magnetic properties of these compounds have been also investigated.
Co-reporter:Fei-Yan Yi, Tian-Hua Zhou, Jiang-Gao Mao
Journal of Molecular Structure 2011 Volume 987(1–3) pp:51-57
Publication Date(Web):22 February 2011
DOI:10.1016/j.molstruc.2010.11.059
Hydrothermal reactions of lead(II) salts with p-sulfophenylarsonic acid (p-HO3S-C6H4-AsO3H2, H3L) afforded two novel lead(II) p-sulfonate-arsonates, namely, Pb3(L)2(H2O)·H2O (1) and Pb3(L)2·6.5H2O (2). Their structures feature two different types of three-dimensional structures. In compound 1, the interconnection of Pb(II) ions by bridging arsonate and sulfonate groups results into a 2D layer parallel to the bc plane. These layers are further cross-linked by phenyl groups into a pillared-layered architecture with small voids occupied by the lattice water. Compound 2 features a 3D open framework based on 1D lead sulfonate-arsonate chains of Pb3O4 clusters along c-axis that are further cross-linked by phenyl groups, forming large tunnels along c-axis which are occupied by a number of lattice water molecules. Introduction of 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) as the auxiliary chelating ligand into the above system led to two new mixed-ligand lead(II) sulfonate-arsonates, namely, Pb(HL)(bipy)·2H2O (3) and Pb(HL)(phen)·2H2O (4). Compounds 3 and 4 display a similar one-dimensional chain in which neighboring Pb2O2 units are bridged by a pair of HL2− anions. There also exists a 1D water chain in compound 3. All four compounds display strong fluorescent emission bands in the green or red light region.
Co-reporter:ChuanFu Sun;BingPing Yang;JiangGao Mao
Science China Chemistry 2011 Volume 54( Issue 6) pp:
Publication Date(Web):2011 June
DOI:10.1007/s11426-011-4289-8
Metal iodates with a lone-pair containing I(V) that is in an asymmetric coordination geometry can form a diversity of unusual structures and many of them are promising new second homonic generation (SHG) materials. They exhibit wide transparency wavelength regions, large SHG coefficients and high optical-damage thresholds as well as moderately high thermal stability. In this paper, the structures and properties of the metal iodates are reviewed. The combination of d0 transition-metal cations with the iodate groups afforded a large number of metal iodates, with cations covering alkali metal, alkaline earth and lanthanide elements. Many of them are noncentrosymmetric (NCS) and display excellent SHG properties due to the additive effects of polarizations from both types of the asymmetric units. Some lanthanide iodates are able to emit strong luminescence in the visible or near-IR regions. The use of transition metal ions with dn (n ≠ 0) electronic configuration into iodate systems can also induce the formation of NCS compounds when the lone pairs of the iodate groups are properly aligned. The dn transition metal cations are normally octahedrally coordinated or in a square-planar coordination geometry. Furthermore, the combination of two different types of lone-pair-containing cations is also an effective strategy to design new SHG materials.
Co-reporter:Bing-Ping Yang, Chun-Li Hu, Xiang Xu, Chuan-Fu Sun, Jian-Han Zhang and Jiang-Gao Mao
Chemistry of Materials 2010 Volume 22(Issue 4) pp:1545
Publication Date(Web):January 12, 2010
DOI:10.1021/cm902902j
The synthesis, crystal structure, and characterizations of a new noncentrosymmetric vanadyl iodate NaVO2(IO3)2(H2O), are reported. NaVO2(IO3)2(H2O) crystallizes in the polar monoclinic space group P21 (No. 4) with a = 9.114(1) Å, b = 5.2146(5) Å, c = 9.216(1) Å, and β = 111.298(8)°. It displays a unique layered structure composed of 1D right-handed helical chains of [(VO2)(IO3)2]− anions along the b-axis that are bridged by sodium(I) ions. The polarity in the structure is imparted by the alignment of the stereochemically active lone pairs of the iodate anions along the b-axis. On the basis of the powder second-harmonic generation (SHG) measurements, NaVO2(IO3)2(H2O) belongs to the phase-matchable class with a very large SHG response of approximately 20 × KH2PO4 (KDP) or about 800 × α-quartz, which is in good agreement with the results from the theoretical calculations.
Co-reporter:Tian-Hua Zhou ; Fei-Yan Yi ; Pei-Xin Li
Inorganic Chemistry 2010 Volume 49(Issue 3) pp:905-915
Publication Date(Web):December 30, 2009
DOI:10.1021/ic901621x
Hydrothermal reactions of lanthanide(III) chlorides with 4-HOOC−C6H4−CH2NHCH2PO3H2 (H3L) at different ligand-to-metal (L/M) ratios afforded nine new lanthanide(III) carboxylate-phosphonates with two types of 3D network structures, namely, LnCl(HL)(H2O)2 (Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Er, 6) and [Ln2(HL)(H2L)(L)(H2O)2]·4H2O (Ln = Nd, 7; Sm, 8; Eu, 9). Compounds 1−6 are isostructural and feature a 3D network in which the LnO7Cl polyhedra are interconnected by bridging CPO3 tetrahedra into 2D inorganic layers parallel to the bc plane. These layers are further cross-linked by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups into a pillared-layered architecture. Compounds 7−9 are also isostructural and feature a 3D open-framework composed of 1D lanthanide(III) phosphonate inorganic slabs which are further bridged by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups, forming large 1D tunnels along the b-axis which are filled by lattice water molecules. Luminescent measurements indicate that compounds 2, 4, and 5 show strong emission bands in red, green, and yellow light region, respectively. Magnetic properties of 2, 3, 5, and 7 have also been studied.
Co-reporter:Fei-Yan Yi, Qi-Pu Lin, Tian-Hua Zhou and Jiang-Gao Mao
Inorganic Chemistry 2010 Volume 49(Issue 7) pp:3489-3500
Publication Date(Web):March 3, 2010
DOI:10.1021/ic100103k
Hydrothermal reactions of manganese(II) salts with o-sulfophenylarsonic acid (o-HO3S−C6H4−AsO3H2, H3L) afforded Mn3(L)2(H2O)3·H2O (1) with a layered structure. When 1,10-phenanthroline (phen), 2,2′-bipyridine (bipy), and 2,2′:6′,2′′-terpyridine (terpy) were used as auxiliary chelating ligands, a series of mixed-ligand manganese(II) sulfonate-arsonates with lower dimensional structures, namely, [Mn(HL)(phen)2]2·8.5H2O (2), Mn(HL)(phen)2(H2O)·2H2O (3), [Mn(HL)(bipy)2][Mn(H2L)(bipy)2](ClO4)·3H2O (4), [Mn(HL)(phen)][Mn(HL)(phen)(H2O)] (5), [Mn2(HL)(phen)4(H2O)](ClO4)2·4H2O (6), [Mn2(HL)(phen)4(H2O)](ClO4)2·H2O (7), Mn2(HL)2(bipy)3(H2O)·H2O (8), [Mn(HL)(terpy)]2 (9), Mn7(OH)2(L)4(phen)8·10H2O·phen (10), and Mn(HL)(bipy)(H2O)·2H2O (11) have been obtained. 2−4 are mononuclear (4 contains two different mononuclear cluster units) whereas 5−9 feature three types of isolated dinuclear cluster units in which the two Mn2+ ions are bridged by one or two sulfonate-arsonate ligands. 10 exhibits an interesting heptanuclear cluster in which the Mn2+ centers are bridged by arsonate, sulfonate groups and hydroxyl anions. 11 features a one-dimensional (1D) chain in which two neighboring Mn2+ centers are bridged by an arsonate group of a sulfonate-arsonate ligand. Magnetic measurements indicate that 1 exhibits an unprecedented spin topology and behaves as a homospin ferrimagnet whereas 2−4 are essentially paramagnetic. 5−9 and 11 are weakly antiferromagnetic.
Co-reporter:Pei-Xin Li ; Chun-Li Hu ; Xiang Xu ; Rui-Yao Wang ; Chuan-Fu Sun
Inorganic Chemistry 2010 Volume 49(Issue 10) pp:4599-4605
Publication Date(Web):April 16, 2010
DOI:10.1021/ic100234e
Explorations of new second-order nonlinear optical (NLO) materials in the KI-MII -IV-O systems led to four novel mixed metal iodates, namely, K2M(IO3)4(H2O)2 (M = Mn, Co, Zn, Mg). The four compounds are isostructural and crystallize in space group I2 which is in the chiral and polar crystal class 2. Their structure features zero-dimensional {M(IO3)4(H2O)2}2− anions that are separated by K+ cations. The M(II) centers are ligated by two aqua ligands in trans fashion and four monodentate iodate anions. The K+ cation is eight-coordinated by two iodate anions in bidentate chelating fashion and four other iodates in a unidentate fashion. Second harmonic generation (SHG) measurements indicate that K2Zn(IO3)4(H2O)2 and K2Mg(IO3)4(H2O)2 display moderate SHG responses that are approximately 2.3 and 1.4 times of KH2PO4 (KDP), respectively, and they are also phase-matchable. The SHG response of K2Co(IO3)4(H2O)2 is much weaker (about 0.3×KDP), and no obvious SHG signal was detected for K2Mn(IO3)4(H2O)2. Results of optical property calculations for the Zn and Mg phases revealed SHG responses of approximately 5.3 and 4.7 times of KDP, respectively, the order of Zn > Mg is in good agreement with the experiment data.
Co-reporter:Pei-Xin Li ; Fang Kong ; Chun-Li Hu ; Na Zhao
Inorganic Chemistry 2010 Volume 49(Issue 13) pp:5943-5952
Publication Date(Web):June 7, 2010
DOI:10.1021/ic100462r
Systematic explorations of the new phases in the PbII/BiIII−TM(d0/d1)−SeIV−O systems by hydrothermal syntheses led to five new quaternary phases whose structures are composed of three different asymmetric building units, namely, Pb2VV2Se2O11 (1), Pb2VIV3Se5O18 (2), Pb2NbV2Se4O15 (3), Bi2VV2Se4O16 (4), and Bi2MoVI2Se2O13 (5). The structure of 1 features a 3D network built by 1D anionic chains of [V2O5(SeO3)2]4− interconnected by Pb2+ ions with six-membered-ring (MR) tunnels along the b axis. The structure of 2 features a 3D anionic framework composed of VIVO6 octahedra corner-sharing with SeO3 anions, with the Pb2+ ions located at the resultant 8-MR tunnels. The oxidation state of the vanadium cation is 4+ due to the partial oxidation of V2O3 by SeO2 at high temperature. The structure of 3 features novel 1D double chains of [Nb2O3(SeO3)4]4− that are interconnected by Pb2+ ions, forming a 3D network with 12-MR tunnels along the c axis. 4 features a 3D framework composed of 2D layers of [Bi2(SeO3)2]2+ and 1D [(VO2)2(SeO3)2]2− double chains. The structure of 5 features a 3D network composed of bismuth(III) selenite with large 10-MR tunnels along the a axis that are occupied by Mo2O10 dimers. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory methods indicate that all five compounds are wide-band-gap semiconductors. Luminescent property measurements for compounds 1−5 and magnetic measurements for compound 2 were also made.
Co-reporter:Chuan-Fu Sun ; Chun-Li Hu ; Xiang Xu
Inorganic Chemistry 2010 Volume 49(Issue 20) pp:9581-9589
Publication Date(Web):September 20, 2010
DOI:10.1021/ic101370v
Three new novel palladium(II) iodates with square-planar PdO4 units, namely, Pd(IO3)2, AgPd(IO3)3, and BaPd(IO3)4, have been successfully hydrothermally synthesized. They represent the first ternary and quaternary palladium(II) iodates and display three different structural types. Pd(IO3)2 exhibits a novel two-dimensional (2D) layered structure in which each PdO4 square further connects with four neighboring ones by four bridging IO3 groups. AgPd(IO3)3 exhibits a unique three-dimensional (3D) network based on unique one-dimensional (1D) [Pd(IO3)3]− anionic chains along the c-axis which are further interconnected by Ag+ cations. BaPd(IO3)4 is isostructural with KAu(IO3)4, and its structure features zero-dimensional (0D) [Pd(IO3)4]2− anionic units that are interconnected by Ba2+ cations. These materials can be polar or non-polar depending on the different alignments of the lone pairs of the I(V) atoms. Pd(IO3)2 and AgPd(IO3)3 are non-polar and centrosymmetric, hence not second-harmonic generation (SHG) active. BaPd(IO3)4 is polar and displays a moderate SHG response of about 0.4× KTP. Thermal analyses, optical, luminescent, and ferroelectric properties as well as electronic structure calculations have also been performed.
Co-reporter:Su-Yun Zhang, Chun-Li Hu, Chuan-Fu Sun, and Jiang-Gao Mao
Inorganic Chemistry 2010 Volume 49(Issue 24) pp:11627-11636
Publication Date(Web):November 23, 2010
DOI:10.1021/ic1020737
Six new novel alkaline-earth metal vanadium(V) or vanadium(IV) selenites and tellurites, namely, Sr2(VO)3(SeO3)5, Sr(V2O5)(TeO3), Sr2(V2O5)2(TeO3)2(H2O), Ba3(VO2)2(SeO3)4, Ba2(VO3)Te4O9(OH), and Ba2V2O5(Te2O6), have been prepared and structurally characterized by single crystal X-ray diffraction analyses. These compounds exhibit six different anionic structures ranging from zero-dimensional (0D) cluster to three-dimensional (3D) network. Sr2(VO)3(SeO3)5 features a 3D anionic framework composed of VO6 octahedra that are bridged by SeO3 polyhedra. The oxidation state of the vanadium cation is +4 because of the partial reduction of V2O5 by SeO2 at high temperature. Ba3(VO2)2(SeO3)4 features a 0D [(VO2)(SeO3)2]3− anion. Sr(V2O5)(TeO3) displays a unique 1D vanadium(V) tellurite chain composed of V2O8 and V2O7 units connected by tellurite groups, forming 4- and 10-MRs, whereas Sr2(V2O5)2(TeO3)2(H2O) exhibits a 2D layer consisting of [V4O14] tetramers interconnected by bridging TeO32− anions with the Sr2+ and water molecules located at the interlayer space. Ba2(VO3)Te4O9(OH) exhibits a one-dimensional (1D) vanadium tellurite chain composed of a novel 1D [Te4O9(OH)]3− chain further decorated by VO4 tetrahedra. Ba2V2O5(Te2O6) also features a 1D vanadium(V) tellurites chain in which neighboring VO4 tetrahedra are bridged by [Te2O6]4− dimers. The existence of V4+ ions in Sr2(VO)3(SeO3)5 is also confirmed by magnetic measurements. The results of optical diffuse-reflectance spectrum measurements and electronic structure calculations based on density functional theory (DFT) methods indicate that all six compounds are wide-band gap semiconductors.
Co-reporter:Fang Kong, Xiang Xu, and Jiang-Gao Mao
Inorganic Chemistry 2010 Volume 49(Issue 24) pp:11573-11580
Publication Date(Web):November 15, 2010
DOI:10.1021/ic101843g
Systematic explorations of new compounds in the LiI−GaIII−TeIV−O system led to two new isomeric ternary gallium tellurites, namely, α-Ga2(TeO3)3 and β-Ga2(TeO3)3, and two new quaternary lithium gallium tellurites, namely, HLi2Ga3(TeO3)6(H2O)6 and Li9Ga13Te21O66. α-Ga2(TeO3)3 is a noncentrosymmetric structure (I4̅3d) and displays a moderately strong second-harmonic-generation response that is comparable with that of KDP (KH2PO4). Its structure features a condensed three-dimensional (3D) network alternatively connected by GaO4 tetrahedra and TeO3 trigonal pyramids via corner sharing. β-Ga2(TeO3)3 is centrosymmetric (P63/m) and features a 3D open framework composed of Ga2O9 dimers bridged by TeO3 groups with one-dimensional (1D) 12-MR channels along the c axis. Although both HLi2Ga3(TeO3)6(H2O)6 and Li9Ga13Te21O66 crystallized in the same space group R3̅, they belong to different structure types. The structure of HLi2Ga3(TeO3)6(H2O)6 can be viewed as the 1D tunnels of the 3D gallium tellurite being occupied by Li+ and H+ ions whereas the structure of Li9Ga13Te21O66 is a complicated 3D framework composed of alternating gallium tellurite layers and GaO6 octahedral layers with Li+ cations being located at the cavities of the structure. Optical diffuse-reflectance spectrum measurements indicate that all four compounds are insulators and transparent in the range of 300−2500 nm.
Co-reporter:Pei-Xin Li and Jiang-Gao Mao
Dalton Transactions 2010 vol. 39(Issue 1) pp:107-112
Publication Date(Web):02 Nov 2009
DOI:10.1039/B916465K
Two new examples of mixed metal copper(I) sulfites, namely, Na3Mn2Cu(SO3)4(H2O)5 (1) and NaMn4Cu(SO3)5(H2O)3 (2), have been synthesized and structurally characterized. The 1D structure of 1 is built from a chain of [Mn2Cu(SO3)4]3− bridged by Na+ ions whereas the structure of 2 features a complicated 3D framework in which Mn8O36 octanuclear clusters are bridged by sulfite anions and copper(I) ions into a 3D [CuMn4(SO3)5(H2O)3]2− network. The eight-coordinated sodium(I) ions are located at the cavities of the 3D structure. In both compounds, the oxygen atoms of the sulfite anion are bonded to Mn(II) ions whereas the sulfur atom is coordinated to the Cu+ ion. Magnetic measurements indicate that there exists antiferromagnetic interactions between Mn(II) centers in both compounds.
Co-reporter:Fei-Yan Yi, Qi-Pu Lin, Tian-Hua Zhou and Jiang-Gao Mao
Crystal Growth & Design 2010 Volume 10(Issue 4) pp:1788-1797
Publication Date(Web):January 21, 2010
DOI:10.1021/cg901463f
Hydrothermal reactions of lanthanide(III) salts with sodium 2,4,6-trisulphonate, Na3L(H2O)3, (1) (L = 2,4,6-trisulfo-C6H2-OH) and 1,10-phenanthroline (phen) led to seven new lanthanide(III) sulfonate hybrids, namely, La(L)(phen)(H2O)3·phen·3H2O (2), Ln2(L)2(phen)2(H2O)5·2phen·8.5H2O (Ln = Pr, 3; Nd, 4), Ln2(L)2(phen)2(H2O)4·2phen·8H2O (Ln = Eu, 5; Gd, 6; Tb, 7), and Nd(L)(phen)(H2O)·phen·H2O (8). 1 features a three-dimensional (3D) network in which the sodium(I) ions are interconnected by chelating and bridging trisulphonate ligands. 2−7 contain [Ln2(L)2(phen)2] dinuclear clusters which are further assembled into 3D supramolecular networks via very weak hydrogen bonds and aromatic packing interactions. 8 features a one-dimensional chain in which two neighboring Nd2O2 dinulear cluster units are further bridged by a pair of sulfonate ligands. 2, 3, 6, and 7 display a broad and strong ligand-centered luminescent emission band in the blue-light region, whereas 4, 5, and 8 exhibit very strong emission bands characteristic of the corresponding lanthanide(III) ions. Magnetic measurements indicate that there is antiferromagnetic interactions between magnetic centers in 3−6 and 8 but ferromagnetic interactions in 7.
Co-reporter:Xiao-Wu Lei, Zhong-Ming Sun, Long-Hua Li, Guo-Hua Zhong, Chun-Li Hu, Jiang-Gao Mao
Journal of Solid State Chemistry 2010 Volume 183(Issue 4) pp:920-926
Publication Date(Web):April 2010
DOI:10.1016/j.jssc.2010.02.004
The title compounds have been obtained by solid state reactions of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction studies. Yb5Ni4Sn10 adopts the Sc5Co4Si10 structure type and crystallizes in the tetragonal space group P4/mbm (No. 127) with cell parameters of a=13.785(4) Å, c=4.492 (2) Å, V=853.7(5) Å3, and Z=2. Yb7Ni4Sn13 is isostructural with Yb7Co4InGe12 and crystallizes in the tetragonal space group P4/m (No. 83) with cell parameters of a=11.1429(6) Å, c=4.5318(4) Å, V=562.69(7) Å3, and Z=1. Both structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are occupied by the Yb atoms. Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic. These results are in agreement with those from temperature-dependent resistivity and magnetic susceptibility measurements.Two new ytterbium nickel stannides, namely, Yb5Ni4Sn10 and Yb7Ni4Sn13, have been synthesized and structurally characterized by single-crystal X-ray diffraction studies. Both their structures feature three-dimensional (3D) frameworks based on three different types of one-dimensional (1D) channels, which are situated by all the Yb atoms. Electronic structure calculations based on density functional theory (DFT) indicate that both compounds are metallic, which are in accordance with the results from temperature-dependent resistivity and magnetic susceptibility measurements.
Co-reporter:Fei-Yan Yi, Qi-Pu Lin, Tian-Hua Zhou, Jiang-Gao Mao
Journal of Molecular Structure 2010 Volume 984(1–3) pp:416-423
Publication Date(Web):15 December 2010
DOI:10.1016/j.molstruc.2010.10.017
Hydrothermal reactions of copper(II) salts with o-sulfophenylarsonic acid (o-HO3S–C6H4–AsO3H2, H3L) led to a layered compound, Cu2.5(L)(OH)2 (1). Introduction of the auxiliary chelating ligands such as 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) and 2,2′:6′,2′′-terpyridine (terpy) led to three new copper(II) sulfonate–arsonates with lower dimensional structures, namely, mononuclear Cu(HL)(bipy)(H2O)·2H2O (2), dinuclear [Cu(HL)(phen)]2·4H2O (3) and one-dimensional Cu(HL)(terpy)·2H2O (4). Magnetic property measurements indicate that 1 exhibits ordinary antiferromagnetic feature, without the geometric spin frustration as expected. 2 shows a typical paramagnetic behavior. There exists antiferromagnetic interactions between the magnetic centers in dimeric 3. 4 displays an antiferromagnetic magnetic exchange interaction propagated via OSO bridges.
Co-reporter:Xiao-Wu Lei, Chun-Li Hu, Jiang-Gao Mao
Journal of Solid State Chemistry 2010 Volume 183(Issue 9) pp:2032-2039
Publication Date(Web):September 2010
DOI:10.1016/j.jssc.2010.07.003
Four new isostructural rare earth manganese stannides, namely RE3MnSn5−x (x=0.16(6), 0.29(1) for RE=Tm, x=0.05(8), 0.21(3) for RE=Lu), have been obtained by reacting the mixture of corresponding pure elements at high temperature. Single-crystal X-ray diffraction studies revealed that they crystallized in the orthorhombic space group Pnma (No. 62) with cell parameters of a=18.384(9)–18.495(6) Å, b=6.003(3)–6.062(2) Å, c=14.898(8)–14.976(4) Å, V=1644.3(14)–1679.0(9) Å3 and Z=8. Their structures belong to the Hf3Cr2Si4 type and feature a 3D framework composed of 1D [Mn2Sn7] chains interconnected by [Sn3] double chains via Sn–Sn bonds, forming 1D large channels based on [Mn4Sn16] 20-membered rings along the b-axis, which are occupied by the rare earth atoms. Electronic structure calculations based on density functional theory (DFT) for idealized “RE3MnSn5” model indicate that these compounds are metallic, which are in accordance with the results from temperature-dependent resistivity measurements.The new isostructural rare earth manganese stannides, namely RE3MnSn5−x (RE=Tm, Lu), have been synthesized by reacting the mixture of the corresponding pure elements and structurally characterized.
Co-reporter:Chuan-Fu Sun ; Chun-Li Hu ; Xiang Xu ; Ji-Bei Ling ; Ting Hu ; Fang Kong ; Xi-Fa Long
Journal of the American Chemical Society 2009 Volume 131(Issue 27) pp:9486-9487
Publication Date(Web):June 22, 2009
DOI:10.1021/ja9030566
By combination of Nb5+ (having a d0 electronic configuration) and the lone-pair-containing iodate anion, a new SHG material, BaNbO(IO3)5, has been prepared. It exhibits a very large SHG response (∼14 times that of KH2PO4 and ∼660 times that of α-SiO2) and is phase-matchable. The material has high thermal stability and a wide transparent region.
Co-reporter:Fei-Yan Yi, Na Zhao, Wei Wu and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 2) pp:628-637
Publication Date(Web):December 10, 2008
DOI:10.1021/ic8016535
Hydrothermal reactions of cadmium(II) or manganese(II) salts with aryl arsenic acids RAsO3H2 (R = C6H5−, H2L1; 3–NO2−4–OH−C6H3−, H3L2) and 1,10-phenanthroline (phen) led to six new cadmium(II) and manganese(II) organo arsonates, namely, Cd(phen)(HL1)2(H2O) (1), M(phen)(H2L2)2 (M = Mn, 2; Cd, 3), [M(phen)2(H2L2)](ClO4)·(H2O) (M = Mn, 4; Cd, 5), and [Mn(phen)2(HL1)](ClO4)·(H2O) (6). The structures of 1, 4, and 5 contain two types of dinuclear clusters, whereas 2 and 3 exhibit 1D chains based on dinuclear M2(μ-O)2 cluster units further bridged by arsonate ligands. Compound 6 features a 1D helical chain in which neighboring two metal centers are bridged by one arsonate ligand. Magnetic property measurements on compounds 2, 4, and 6 indicate that there exist very weak antiferromagnetic interactions between magnetic centers in all three compounds. Compounds 1−6 display typical ligand-centered fluorescence emission bands.
Co-reporter:Ting Hu, Li Qin, Fang Kong, Yong Zhou and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 5) pp:2193-2199
Publication Date(Web):February 3, 2009
DOI:10.1021/ic8022375
Hydrothermal reactions of lanthanide oxide, lead chloride, I2O5, and H2O at 200 °C led to four novel quaternary compounds, namely, Ln3Pb3(IO3)13(μ3−O) (Ln = La−Nd). They are isostructural, and their structures feature a complicated 3D network composed of LaO9 and PbO6 polyhedra interconnected by asymmetric IO3 groups. Ln3Pb3(IO3)13(μ3−O) (Ln = La, Pr, Nd) display moderate second harmonic generation efficiencies of about 2.0, 1.0, and 0.8 times the value of KH2PO4, respectively. These compounds are thermally stable up to 520 °C. Luminescence measurements indicate that Ln3Pb3(IO3)13(μ3−O) (Ln = Ce, Pr, Nd) exhibit strong emission bands in the visible or near IR region. Magnetic studies indicate that there exist significant antiferromagnetic interactions between magnetic centers in Ln3Pb3(IO3)13(μ3−O) (Ln = Pr, Nd).
Co-reporter:Xiao-Wu Lei, Guo-Hua Zhong, Long-Hua Li, Chun-Li Hu, Min-Jie Li and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 6) pp:2526-2533
Publication Date(Web):February 9, 2009
DOI:10.1021/ic8019765
The title three compounds have been synthesized by solid state reactions at high temperatures, with excess indium as flux, and structurally characterized by single-crystal X-ray diffraction studies. Eu3Co2In15 forms a new structure type and crystallizes in the tetragonal space group P4/mbm (No. 127), whereas KM2In9 (M = Co, Ni) in the BaFe2Al9 type crystallizes in the hexagonal space group P6/mmm (No. 191). Their structures all feature a three-dimensional anionic framework based on 1D [MIn6] single cluster chains composed of face-sharing [MIn9] clusters. In Eu3Co2In15, two adjacent [CoIn6] single cluster chains form a [Co2In11] double cluster chain via corner-sharing In atoms as well as In−In bonds; the latter chains are further interconnected by additional indium atoms via In−In bonds into a complicated 3D framework, forming two types of tunnels along the c-axis, which are filled by the europium atoms. In KM2In9, the [MIn6] single cluster chains are directly interconnected via corner sharing and exo In−In bonds into a 3D framework with the K+ ions encapsulated in the 1D tunnels along the c-axis. Band structure calculations of three compounds based on density functional theory methods indicate that all three compounds are metallic.
Co-reporter:Pei-Xin Li, Chun-Li Hu, Qi-Pu Lin, Na Zhao and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 12) pp:5454-5461
Publication Date(Web):May 20, 2009
DOI:10.1021/ic900487j
Two types of new organically templated mixed-metal sulfites, namely, [H2pip][NaZn2Cu(SO3)4] (1) and [H2pip][CdCu4(SO3)4] (2) (pip = piperazine), have been synthesized under hydrothermal conditions and structurally characterized. Both compounds exhibit a novel 3D mixed-metal inorganic framework with organic template molecules occupying the tunnels of the inorganic skeleton. Compound 1 features a 2D Zn2Cu(SO3)43− layer parallel to the ac plane in which the 1D chains of Zn(SO3)22− anions along the c axis are interconnected with the Cu+ ions via Cu−S bonds. Neighboring Zn2Cu(SO3)43− layers are further interconnected by bridging Na+ ions via Na−O−S bonds into a 3D network, forming 1D tunnels along the a axis which are occupied by the doubly protonated piperazine cations. Compounds 2 features a novel 3D inorganic framework of CdCu4(SO3)42− with 2D layers based on Cu4(SO3)44− cubanelike clusters. The cluster layers are further interconnected by Cd(II) ions, forming 1D tunnels of eight-membered rings along the c axis in which the piperazine template cations are located. Luminescent property measurements as well as band structure calculations based on density functional theory methods were also made.
Co-reporter:Fang Kong, Qi-Pu Lin, Fei-Yan Yi and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 14) pp:6794-6803
Publication Date(Web):June 18, 2009
DOI:10.1021/ic900756u
Four new gallium(III)/indium(III), copper(II), selenium(IV) oxides, namely, Ga2Cu(SeO3)4 (1), Ga2CuO(SeO3)3 (2), and M2Cu3(SeO3)6 (M = Ga 3, In 4), have been synthesized by hydrothermal or high-temperature solid-state reactions. The structure of Ga2Cu(SeO3)4 (1) features a 2D layer of corner-sharing GaO6 and CuO6 octahedra with the SeO3 groups hanging on both sides of the 2D layer. Ga2CuO(SeO3)3 (2) features a pillared layered structure in which the 1D Cu(SeO3)34− chains act as the pillars between 2D layers formed by corner- and edge-sharing GaOn (n = 4, 5) polyhedra. Although the chemical compositions of M2Cu3(SeO3)6 (M = Ga 3, In 4) are comparable, they belong to two different structural types. Ga2Cu3(SeO3)6 (3) exhibits a pillared layered structure built by [Ga2Cu3(SeO3)4]4+ thick layers with Se(3)O32− groups as pillars. The structure of In2Cu3(SeO3)6 (4) features a 3D network composed of [In2(SeO3)2]2+ layers and [Cu3(SeO3)4]2− layers interconnected through Se−O−Cu and In−O−Cu bridges, exhibiting 8-MR helical tunnels along the a-axis. Results of magnetic property measurements indicate that there are considerable antiferromagnetic interactions between copper(II) centers in Ga2CuO(SeO3)3 (2) and M2Cu3(SeO3)6 (M = Ga 3, In 4). Interestingly, Ga2Cu3(SeO3)6 (3) behaves as a weak ferromagnet below the critical temperature of Tc = 15 K. Further magnetic studies indicate that the compound is a canted antiferromagnet with a large canting angle of about 7.1°.
Co-reporter:Su-Yun Zhang, Hai-Long Jiang, Chuan-Fu Sun and Jiang-Gao Mao
Inorganic Chemistry 2009 Volume 48(Issue 24) pp:11809-11820
Publication Date(Web):November 17, 2009
DOI:10.1021/ic901855x
Five new transition metal molybdenum(VI) selenites or tellurites, namely, TM(MoO3)(SeO3)(H2O) (TM = Mn, Co), Fe2(Mo2O7)(SeO3)2(H2O), Cu2(MoO4)(SeO3), and Ni3(MoO4)(TeO3)2, have been prepared and structurally characterized. They belong to five different types of structures. Mn(MoO3)(SeO3)(H2O) and Ni3(MoO4)(TeO3)2 are non-centrosymmetric and crystallize in the orthorhombic space groups Pmc21 and P212121, respectively, whereas Co(MoO3)(SeO3)(H2O), Fe2(Mo2O7)(SeO3)2(H2O), and Cu2(MoO4)(SeO3) are centrosymmetric and crystallize in P1̅, C2/c, P21/c, respectively. The Mo6+ cations in Mn(MoO3)(SeO3)(H2O), Co(MoO3)(SeO3)(H2O), and Fe2(Mo2O7)(SeO3)2(H2O) are in severely distorted octahedral geometry whereas those in Cu2(MoO4)(SeO3) and Ni3(MoO4)(TeO3)2 are in a slightly distorted tetrahedral geometry. Second-Harmonic Generation (SHG) measurements revealed that (MoO3)(SeO3)(H2O) displays a moderate SHG signal of about 3 × KH2PO4 (KDP) whereas the SHG response of Ni3(MoO4)(TeO3)2 is much weaker than that of KDP.
Co-reporter:Jun-Ling Song, Fei-Yan Yi and Jiang-Gao Mao
Crystal Growth & Design 2009 Volume 9(Issue 7) pp:3273
Publication Date(Web):May 7, 2009
DOI:10.1021/cg900010z
Hydrothermal reactions of lanthanide nitrates with aminodiphosphonate ligand (H2O3PCH2)2−N−CH2−C6H4−COOH, H5L1) and squaric acid afforded a series of isostructural lanthanide(III) squarato-phosphonates, namely, Ln(HL2) (Ln = La, 1; Pr, 2; Nd, 3; Eu, 4; Gd, 5; Tb, 6; Er, 7) (H4L2 = HOOC−C6H4−CH2−N(C4O3H)(CH2PO3H2)), in which a new multifunctional squarato-phosphonate ligand (H4L2) was formed by in situ condensation reaction between the two types of organic ligands. The seven-coordinated lanthanide(III) ions in these compounds are bridged by the squarato-aminophosphonate moieties of the {HL2}3− anions into a double layer. Each {HL2}3− anion acts as septadentate metal linker, bridging with seven lanthanide ions by using one carboxylate oxygen, three squarato, and three phosphonate oxygens. These double layers are further cross-linked via the coordination of the carboxylate groups into a pillared layered architecture. The Eu, Tb, and Nd compounds exhibit strong luminescence in red light, green light, and near-IR regions, respectively.
Co-reporter:Xiao-Wu Lei, Guo-Hua Zhong, Chun-Li Hu, Jiang-Gao Mao
Journal of Alloys and Compounds 2009 Volume 485(1–2) pp:124-131
Publication Date(Web):19 October 2009
DOI:10.1016/j.jallcom.2009.06.079
Single crystals of Y7Co6Sn23 and RE5Co6Sn18 (RE = Sc, Ho) have been obtained by solid-state reactions of the corresponding pure elements in welded tantalum tubes at high temperature. Their crystal structures have been established by single-crystal X-ray diffraction studies. Y7Co6Sn23 belongs to the Ho7Co6Sn23 type and crystallizes in the trigonal space group P-3m1 (No. 164) whereas RE5Co6Sn18 (RE = Sc, Ho) adopt the Tb5Rh6Sn18 type structure and crystallizes in the tetragonal space group I41/acd (No. 142). Their structures all feature a three-dimensional (3D) anionic framework based on [CoSn6] trigonal prisms. The structure of Y7Co6Sn23 is made from the ordinal stacking one type of 2D slab composed of the same [CoSn6] trigonal prisms via corner-sharing, forming two types of narrow tunnels along the c-axis, which are occupied by Y or residual Sn atoms. The 3D structure of RE5Co6Sn18 is built up from alternately stacking two types of 2D slabs, which are composed of different [CoSn6] trigonal prisms via corner-sharing and Sn–Sn bonds, respectively. The RE and residual Sn atoms are located in the spacers of the 3D framework. Band structure calculations indicate that Y7Co6Sn23 and Sc5Co6Sn18 are metallic.
Co-reporter:Min-Jie Li, Chun-Li Hu, Xiao-Wu Lei, Yong Zhou, Jiang-Gao Mao
Journal of Solid State Chemistry 2009 Volume 182(Issue 5) pp:1245-1251
Publication Date(Web):May 2009
DOI:10.1016/j.jssc.2009.02.020
Three new ternary potassium(I) zinc(II) or cadmium(II) tellurides, namely, K2Cd2Te3, K6CdTe4 and K2ZnTe2, were synthesized by solid-state reactions of the mixture of pure elements of K, Cd (or Zn) and Te in Nb tubes at high temperature. K2Cd2Te3 belongs to a new structure type and its structure contains a novel two-dimensional [Cd2Te3]2− layers perpendicular to the b-axis. K(5) cation is located at the center of five member rings of the 2D [Cd2Te3]2− layer, whereas other K+ cations occupy the interlayer space. K6CdTe4 with a K6HgS4 type structure features a “zero-dimensional” structure composed of isolated CdTe4 tetrahedra separated by the K+ ions. K2ZnTe2 in the K2ZnO2 structural type displays 1D [ZnTe2]2− anionic chains of edge sharing [ZnTe4] tetrahedra separated by the potassium(I) ions. K2Cd2Te3, K6CdTe4 and K2ZnTe2 revealed a band gap of 1.93, 2.51 and 3.0 eV, respectively.Three new semiconducting K–Zn(Cd)–Te phases were synthesized. They feature 2D, 1D or 0D anionic structure made of corner- and edge-sharing or isolated MTe4 tetrahedra.
Co-reporter:Jiang-Gao Mao ; Hai-Long Jiang ;Fang Kong
Inorganic Chemistry 2008 Volume 47(Issue 19) pp:8498-8510
Publication Date(Web):September 29, 2008
DOI:10.1021/ic8005629
Metal selenites and tellurites are a class of very important compounds. In this paper, the structures and properties of metal selenites or tellurites combining with transition-metal (TM) ions with the d0 electronic configuration or tetrahedral MO4 building blocks of post-transition main-group elements were reviewed. Most compounds in the alkali or alkaline-earth−d0 TM−SeIV (or TeIV)−O systems exhibit extended anionic architectures composed of distorted octahedra of (d0) TM cations and tellurite or selenite groups. The distortion of the octahedron is always away from the lone-pair cation, and some of them exhibit excellent second-order nonlinear optical properties due to the adductive effects of two types of bond polarizations. Because of the high coordination number of LnIII ions, most of compounds in the Ln−d0 TM−SeIV (or TeIV)−O systems are not second-harmonic-generation active; however, they are able to emit strong luminescence in the visible or near-IR region; also in most cases, the d0 TM cations are in tetrahedral geometry and are well separated from selenite or tellurite groups. It is also interesting to note that the selenite group is normally “isolated”, whereas the TeOx (x = 3−5) can be polymerized into a variety of discrete polynuclear anionic clusters or extended architectures via Te−O−Te bridges.
Co-reporter:Hai-Long Jiang, Fang Kong, Yang Fan and Jiang-Gao Mao
Inorganic Chemistry 2008 Volume 47(Issue 16) pp:7430-7437
Publication Date(Web):June 24, 2008
DOI:10.1021/ic800638e
Two new metal selenites with a combination of vanadium(IV) or vanadium(V) cations, namely, ZnVSe2O7 and Cd6V2Se5O21, have been synthesized by hydrothermal and high-temperature solid-state reactions, respectively. The structure of ZnVSe2O7 features a 3D network of vanadium(IV) selenite with 1D tunnels occupied by zinc(II) ions. The 3D network of vanadium(IV) selenite is formed by corner-sharing VIVO6 octahedral chains bridged by selenite groups. In Cd6V2Se5O21, the interconnection of cadmium(II) ions by bridging and chelating selenite groups led to a 3D framework with large tunnels along the b axis, and the 1D chains of corner-sharing VVO4 tetrahedra are inserted in the above large tunnels and are bonded to the cadmium selenite framework via Cd−O−V bridges. Both compounds exhibit broad emission bands in the blue-light region. Results of magnetic property measurements show there is significant antiferromagnetic interaction between V4+ centers in ZnVSe2O7. The electronic structure calculations for both compounds have been also performed.
Co-reporter:Fang Kong ; Hai-Long Jiang ; Ting Hu
Inorganic Chemistry 2008 Volume 47(Issue 22) pp:10611-10617
Publication Date(Web):October 17, 2008
DOI:10.1021/ic801292p
Two novel alkali(I) borogermanates with noncentrosymmetric structures, namely, CsB3GeO7 and K2B2Ge3O10, have been synthesized by high-temperature solid-state reactions in a platinum crucible. The structure of CsB3GeO7 features a novel three-dimensional (3D) framework composed of cyclic B3O75− groups that are interconnected by Ge(IV) cations, whereas the structure of K2B2Ge3O10 is a new 3D network based on cap-shaped [Ge3B2O14]10− clusters that are interconnected via Ge−O−B bridges. CsB3GeO7 exhibits a second-harmonic generation (SHG) response that is about 1.5 times that of KDP (KH2PO4), whereas the SHG signal of K2B2Ge3O10 is very weak. Both compounds are insulators and transparent in the range of 300−5000 nm. The electronic structure calculations for both compounds also have been performed.
Co-reporter:Bing-Ping Yang ; Andrey V. Prosvirin ; Ya-Qin Guo
Inorganic Chemistry 2008 Volume 47(Issue 5) pp:1453-1459
Publication Date(Web):January 29, 2008
DOI:10.1021/ic701351x
A new cobalt(II) carboxylate−phosphonate, namely, Co[HO2C(CH2)3NH(CH2PO3H)2]2, with a layered architecture has been synthesized by hydrothermal reactions. The Co(II) ion in the title compound is octahedrally coordinated by six phosphonate oxygen atoms from four carboxylate phosphonate ligands. Neighboring CoO6 octahedra are interconnected by phosphonate groups into a 2D layer with a 4,4-net topology. Adjacent layers are further cross-linked via hydrogen bonds between the noncoordinate carboxylate groups and noncoordinate phosphonate oxygens. The ac and dc magnetic susceptibility and magnetization measurements indicate that Co[HO2C(CH2)3NH(CH2PO3H)2]2 is a canted antiferromagnet with Tc = 8.75 K.
Co-reporter:Ya-Qin Guo, Bing-Ping Yang, Jun-Ling Song and Jiang-Gao Mao
Crystal Growth & Design 2008 Volume 8(Issue 2) pp:600
Publication Date(Web):January 8, 2008
DOI:10.1021/cg700735m
Three zinc(II) phosphonate cluster compounds have been hydrothermally synthesized and structurally characterized. Compound 1 consists of a centered {Zn6(Zn)L6}4− core and two {Zn(Phen)2(H2O)2}2+ countercations (L = N-(phosphonomethyl)pipecolinic acid, O3PCH2−NC5H9−CO2). The {Zn6(Zn)L6}4− core in compound 2 or 3 is covalently bonded to two Zn(H2O)42+ or {Zn(2,2′-bipy)(H2O)3}2+ cations through the coordination of two additional carboxylate oxygen atoms to form a nonanuclear cluster.
Co-reporter:Pei-Xin Li and Jiang-Gao Mao
Crystal Growth & Design 2008 Volume 8(Issue 9) pp:3385-3389
Publication Date(Web):July 18, 2008
DOI:10.1021/cg800341f
Two novel organically templated 3d−4f mixed metal sulfites, namely, [H2pip][Ln4Cu4(SO3)8Br2(H2O)6] (Ln = Eu, 1; Gd, 2; pip = piperazine) have been synthesized and structurally characterized. Compounds 1 and 2 are isostructural and feature a 2D inorganic anion layer of [Ln4Cu4(SO3)8Br2(H2O)6]2−. Among two unique lanthanide(III) ions in the asymmetric unit, one is eight coordinated by seven oxygen atoms from six sulfite groups (five of them in unidentate fashion and one in bidentate chelating fashion) and an aqua ligand; the other one is eight-coordinated by six oxygen atoms from five sulfite groups (four of them in unidentate fashion and one in bidentate chelating fashion) and two aqua ligands. Cu(1) is four coordinated by two S and one O from three SO32− anions, as well as a Br anion, and Cu(2) is three coordinated by one S and one O atom from two SO32− anions, as well as a Br anion. The Ln(III) ions and Cu(I) ions are interconnected by sulfite anions and Br anions to form a layered structure. The piperazine molecules are located at the interlayer spaces. Magnetic properties for both compounds were also studied.
Co-reporter:Hai-Long Jiang, Jiang-Gao Mao
Journal of Solid State Chemistry 2008 Volume 181(Issue 2) pp:345-354
Publication Date(Web):February 2008
DOI:10.1016/j.jssc.2007.12.007
Two new quaternary strontium selenium(IV) and tellurium(IV) oxychlorides, namely, Sr3(SeO3)(Se2O5)Cl2 and Sr4(Te3O8)Cl4, have been prepared by solid-state reaction. Sr3(SeO3)(Se2O5)Cl2 features a three-dimensional (3D) network structure constructed from strontium(II) interconnected by Cl−, SeO32− as well as Se2O52− anions. The structure of Sr4(Te3O8)Cl4 features a 3D network in which the strontium tellurium oxide slabs are interconnected by bridging Cl− anions. The diffuse reflectance spectrum measurements and results of the electronic band structure calculations indicate that both compounds are wide band-gap semiconductors.Solid-state reactions of SrO, SrCl2, and SeO2 or TeO2 in different molar ratios and under different temperatures lead to two new strontium selenium(IV) or tellurium(IV) oxychlorides with two different types of structures, namely, Sr3(SeO3)(Se2O5)Cl2 and Sr4(Te3O8)Cl4. Both compounds are wide band-gap semiconductors based on the diffuse reflectance spectra and the electronic band structures.Figure optionsDownload full-size imageDownload as PowerPoint slide
Co-reporter:Ting Hu, Ji-Bei Lin, Fang Kong, Jiang-Gao Mao
Inorganic Chemistry Communications 2008 Volume 11(Issue 9) pp:1012-1014
Publication Date(Web):September 2008
DOI:10.1016/j.inoche.2008.05.019
Hydrothermal reaction of V2O5 and Mg(BO2)2(H2O) in H2O afforded a novel magnesium vanadate with a non-centrosymmetric structure, Mg7V4O16(OH)2(H2O). The structure of Mg7V4O16(OH)2(H2O) features a novel 3D openframe network of magnesium(II) oxide with tunnels along c-axis based on 6- and 12-member rings (MR), the V(2)O4 tetrahedra are located at 6-MR tunnels whereas V(1)O4 tetrahedra and the 1D chains composed of the face-sharing Mg(1)O6 octahedra are located at the 12-MR tunnels.Hydrothermal reaction of V2O5 and Mg(BO2)2(H2O) in H2O afforded a novel magnesium vanadate with a non-centrosymmetric structure, Mg7V4O16(OH)2(H2O). Its structure features a novel 3D openframe network of magnesium(II) oxide futher decorated by VO4 tetrahedra and 1D chains of face-sharing MgO6 octahedra.
Co-reporter:Xiao-Wu Lei, Guo-Hua Zhong, Min-Jie Li, Jiang-Gao Mao
Journal of Solid State Chemistry 2008 Volume 181(Issue 9) pp:2448-2455
Publication Date(Web):September 2008
DOI:10.1016/j.jssc.2008.05.036
Two new ternary ytterbium transition metal stannides, namely, Yb3CoSn6 and Yb4Mn2Sn5, have been obtained by solid-state reactions of the corresponding pure elements in welded tantalum tubes at high temperature. Their crystal structures have been established by single-crystal X-ray diffraction studies. Yb3CoSn6 crystallizes in the orthorhombic space group Cmcm (no. 63) with cell parameters of a=4.662(2), b=15.964(6), c=13.140(5) Å, V=978.0(6) Å3, and Z=4. Its structure features a three-dimensional (3D) open-framework composed of unusual [CoSn3] layers interconnected by zigzag Sn chains, forming large tunnels along the c-axis which are occupied by the ytterbium cations. Yb4Mn2Sn5 is monoclinic space group C2/m (no. 12) with cell parameters of a=16.937(2), b=4.5949(3), c=7.6489(7) Å, β=106.176(4)°, V=571.70(8) Å3, and Z=2. It belongs to the Mg5Si6 structure type and its anionic substructure is composed of parallel [Mn2Sn2] ladders interconnected by unusual zigzag [Sn3] chains, forming large tunnels along the c-axis, which are filled by the ytterbium cations. Band structure calculations based on density function theory methods were also made for both compounds.Yb3CoSn6 and Yb4Mn2Sn5 have been prepared and structurally characterized. Yb3CoSn6 features a 3D open-framework composed of novel [CoSn3] layers interconnected by the zigzag Sn chains whereas the anionic substructure of Yb4Mn2Sn5 is composed of parallel [Mn2Sn2] ladders interconnected by the unusual one-dimensional (1D) chains formed by linear [Sn3] trimers.
Co-reporter:Ya-Qin Guo, Si-Fu Tang, Bing-Ping Yang, Jiang-Gao Mao
Journal of Solid State Chemistry 2008 Volume 181(Issue 10) pp:2713-2718
Publication Date(Web):October 2008
DOI:10.1016/j.jssc.2008.06.043
Hydrothermal reactions of different lanthanide(III) salts with an amino-diphosphonate ligand (H4L=C6H5CH2N(CH2PO3H2)2) led to two series of lanthanide phosphonates, namely, Ln(H2L)(H3L) (Ln=La, 1; Pr, 2; Nd, 3; Sm, 4; Eu, 5; Gd, 6; Tb, 7). Compounds 1–5 feature a one-dimensional (1D) chain structure in which dimers of two edge-sharing LnO8 polyhedra are interconnected by bridging phosphonate groups, such 1D arrays are further interlinked via strong hydrogen bonds between non-coordinated phosphonate oxygen atoms into a two-dimensional (2D) layer with the phenyl groups of the ligands orientated toward the interlayer space. Compounds 6 and 7 also show a different 1D array in which the LnO6 octahedra are bridged by phosphonate groups via corner-sharing, such chains are also further interlinked by hydrogen bonds into a 2D supramolecular layer. Compounds 5 and 7 emit red and green light with a lifetime of 2.1 and 3.7 ms, respectively.Two series of luminescent lanthanide phosphonates have been synthesized and structurally characterized. Their structures feature two different types of 2D sumpramolecular layers based on two types of 1D arrays interlinked via strong hydrogen bonds.
Co-reporter:Hai-Long Jiang;Shu-Ping Huang;Yang Fan ;Wen-Dan Cheng
Chemistry - A European Journal 2008 Volume 14( Issue 6) pp:1972-1981
Publication Date(Web):
DOI:10.1002/chem.200701440
Abstract
Solid-state reactions of zinc(II) or cadmium(II) oxide, V2O5, and TeO2 at high temperature led to two novel quaternary compounds, namely, Zn3V2TeO10 and Cd4V2Te3O15. The structure of Zn3V2TeO10 is a complicated three-dimensional (3D) network constructed by the interconnection of ZnO5, ZnO6, VO4, and TeO4 polyhedra via corner- and edge-sharing. Cd4V2Te3O15 with an acentric structure features a 3D network in which the cadmium tellurite layers are further interconnected by both “isolated” VO4 tetrahedra and one-dimensional (1D) vanadium oxide helical chains. Cd4V2Te3O15 displays a second harmonic generation (SHG) efficiency of about 1.4 times that of KH2PO4 (KDP). Both compounds are direct band-gap semiconductors and are transparent in the range of 0.6–10.0 μm. Measurements of luminescence indicate that both compounds exhibit broad emission bands in the blue-light region.
Co-reporter:Zi-Yi Du;Hai-Bing Xu;Xiu-Ling Li
European Journal of Inorganic Chemistry 2007 Volume 2007(Issue 28) pp:
Publication Date(Web):7 AUG 2007
DOI:10.1002/ejic.200700463
Five new lead(II) sulfonate-phosphonates, namely [Pb3(L)2(H2O)2]·4H2O (1), [Pb(HL)(phen)]·H2O (2), [Pb6(L)4(phen)8]·3H2O (3), [Pb6(L)4(phen)10]·2H2O (4), and [Pb6(L)4(4,4′-bipy)(H2O)2]·2H2O (5; H3L = m-HO3S-C6H4-PO3H2, phen = 1,10-phenanthroline, 4,4′-bipy = 4,4′-bipyridine) have been prepared and structurally characterized. Compound 1 features a novel 3D framework in which 1D chains of Pb3O4 cluster units are further bridged by sulfonate-phosphonate ligands, whereas compound 2 features a layer structure in which 1D chains of Pb2O4 clusters are further bridged by sulfonate-phosphonate ligands. Compounds 3 and 4 represent the first zero-dimensional lead(II) phosphonates and feature novel isolated hexanuclear lead(II) clusters in which six PbII ions are bridged by two tetradentate and two pentadentate phosphonate groups. Compound 5 features a 3D framework that is similar to that in compound 1 despite the different coordination modes for some sulfonate groups of the ligands. The main difference is that an aqua ligand in compound 1 is replaced by a nitrogen atom of the 4,4′-bipy ligand, which results in the splitting of the large cavities in compound 1 into two small apertures in compound 5. Compounds 1 and 5 exhibit strong broad blue fluorescent emission bands at 398 and 420 nm, respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
Co-reporter:Hai-Long Jiang, Fang Kong, Jiang-Gao Mao
Journal of Solid State Chemistry 2007 Volume 180(Issue 5) pp:1764-1769
Publication Date(Web):May 2007
DOI:10.1016/j.jssc.2007.04.002
A new quaternary lanthanide alkaline–earth tellurium(IV) oxide, La2Ba(Te3O8)(TeO3)2, has been prepared by the solid-state reaction and structurally characterized. The compound crystallizes in monoclinic space group C2/c with a=19.119(3), b=5.9923(5), c=13.2970(19) Å, β=107.646(8)°, V=1451.7(3) Å3 and Z=4. La2Ba(Te3O8)(TeO3)2 features a 3D network structure in which the cationic [La2Ba(TeO3)2]4+ layers are cross-linked by Te3O84− anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La2Ba(Te3O8)(TeO3)2 is a wide band-gap semiconductor.A new quaternary lanthanide alkaline–earth tellurium(IV) oxide, La2Ba(Te3O8)(TeO3)2, has been prepared by the solid-state reaction and structurally characterized. The structure of La2Ba(Te3O8)(TeO3)2 is 3D network in which the cationic [La2Ba(TeO3)2]4+ layers are cross-linked by Te3O84− anions. Both band structure calculation by the DFT method and optical diffuse reflectance spectrum measurements indicate that La2Ba(Te3O8)(TeO3)2 is a wide band-gap semiconductor.
Co-reporter:Xue-Li Cao, Chun-Li Hu, Xiang Xu, Fang Kong and Jiang-Gao Mao
Chemical Communications 2013 - vol. 49(Issue 85) pp:NaN9967-9967
Publication Date(Web):2013/08/29
DOI:10.1039/C3CC45747H
The replacement of NbO6 octahedra in Pb2NbO2(SeO3)2Cl by the TiO5F octahedra in Pb2TiOF(SeO3)2Cl induced a very large SHG enhancement from 2.3 × to 9.6 × KDP (KH2PO4), and both materials are type-I phase matchable. Theoretical calculations based on DFT methods indicate that the inclusion of F− anions in the d0-TM octahedral coordination unit has a great impact on the band structure and the SHG enhancement of the material.
Co-reporter:Chuan-Fu Sun, Chun-Li Hu and Jiang-Gao Mao
Chemical Communications 2012 - vol. 48(Issue 35) pp:NaN4222-4222
Publication Date(Web):2012/03/05
DOI:10.1039/C2CC30326D
A new polar material containing two types of stereoactive lone-pairs has been synthesized. The unique parallel alignment of the stereoactive lone-pairs on Pb2+ cations and the synergistic effect of two types of stereoactive lone-pairs on I5+ and Pb2+ cations make it exhibit a very large second-harmonic generation response of about 8 × KDP (KH2PO4).
Co-reporter:Tian-Hua Zhou, Jian Zhang, Hai-Xia Zhang, Rui Feng and Jiang-Gao Mao
Chemical Communications 2011 - vol. 47(Issue 31) pp:NaN8864-8864
Publication Date(Web):2011/07/11
DOI:10.1039/C1CC12914G
An unusual ligand-conformation driving chiral generation and symmetry-breaking crystallization occurred simultaneously in the formation of a layered zinc(II) arsonate Zn(Hcapa)(4,4′-bipy) (1P) and its enantiomorph (1M) without any chiral sources, indicating that the asymmetrical crystallization of the coordination polymer from achiral precursors may be induced by the conformation control of the ligand.
Co-reporter:Pei-Xin Li and Jiang-Gao Mao
Dalton Transactions 2010 - vol. 39(Issue 1) pp:NaN112-112
Publication Date(Web):2009/11/02
DOI:10.1039/B916465K
Two new examples of mixed metal copper(I) sulfites, namely, Na3Mn2Cu(SO3)4(H2O)5 (1) and NaMn4Cu(SO3)5(H2O)3 (2), have been synthesized and structurally characterized. The 1D structure of 1 is built from a chain of [Mn2Cu(SO3)4]3− bridged by Na+ ions whereas the structure of 2 features a complicated 3D framework in which Mn8O36 octanuclear clusters are bridged by sulfite anions and copper(I) ions into a 3D [CuMn4(SO3)5(H2O)3]2− network. The eight-coordinated sodium(I) ions are located at the cavities of the 3D structure. In both compounds, the oxygen atoms of the sulfite anion are bonded to Mn(II) ions whereas the sulfur atom is coordinated to the Cu+ ion. Magnetic measurements indicate that there exists antiferromagnetic interactions between Mn(II) centers in both compounds.
Co-reporter:Fang Kong, Chun-Li Hu, Xiang Xu, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2012 - vol. 41(Issue 18) pp:NaN5695-5695
Publication Date(Web):2012/02/22
DOI:10.1039/C2DT12437H
Four new quaternary molybdenum selenites, namely, HRb3(Mo5O15)(SeO3)2(H2O)21, α-Rb4Mo5O15(SeO3)2(H2O)22, β-Rb4Mo5O15(SeO3)2(H2O)23 and K4Mo5O15(SeO3)2(H2O)24 were synthesized by hydrothermal reactions. All of the four compounds feature a zero-dimensional (0D) [(Mo5O15)(SeO3)2]4− anionic unit composed of a five-member MoO6 octahedral ring capped by two SeO32− trigonal pyramids, with the Rb+/K+ or/and H+ cations and water molecules acting as spacers and keeping charge balance. Although these compounds exhibit similar chemical formula, their structures are slightly different. HRb3(Mo5O15)(SeO3)2(H2O)21 crystallizes in a polar space group (Pca21). α-Rb4Mo5O15(SeO3)2(H2O)22 crystallizes in a centrosymmetric (CS) space group (P21/n) whereas β-Rb4Mo5O15(SeO3)2(H2O)23 and K4Mo5O15(SeO3)2(H2O)24 are isomorphous, crystallize in a chiral space group (C2). The chiral structures of 3 and 4 contain two similar polyanions of [Mo5O15(SeO3)2]4− with opposite handedness. Second-harmonic-generation (SHG) measurements indicate that 1, 3 and 4 are all SHG-active. Compound 1 displays a weak SHG response of about 20% of that of KDP (KH2PO4) and is phase-matchable whereas the SHG responses of 3 and 4 are very weak (less than 5% of that of KDP). Thermal analyses and optical property measurements have also been performed.
Co-reporter:Su-Yun Zhang, Chun-Li Hu, Pei-Xin Li, Hai-Long Jiang and Jiang-Gao Mao
Dalton Transactions 2012 - vol. 41(Issue 31) pp:NaN9542-9542
Publication Date(Web):2012/06/11
DOI:10.1039/C2DT30560G
Four new lead(II) or bismuth(III) selenites and a tellurite, namely, Pb3(TeO3)Cl4, Pb3(SeO3)2Br2, Pb2Cd3(SeO3)4I2(H2O), Pb2Ge(SeO3)4 and BiFe(SeO3)3, have been prepared and structurally characterized by single crystal X-ray diffraction (XRD) analyses. These compounds exhibit five different types of structures. The structure of Pb3(TeO3)Cl4 features a three-dimensional (3D) lead(II) chloride network with tellurite anions filling in the 1D tunnels of Pb4 4-member rings (MRs) along the c-axis. Pb3(SeO3)2Br2 contains a 3D network composed of lead(II) selenite layers interconnected by bromide anions. Pb2Cd3(SeO3)4I2(H2O) is a 3D structure based on 2D cadmium(II) selenite layers which are further connected by 1D lead(II) iodide ladder chains with lattice water molecules located at the 1D tunnels of the structure. Pb2Ge(SeO3)4 features a 3D framework constructed by the alternate arrangement of lead(II) selenite layers and germanium(IV) selenite layers in the [100] direction. The structure of BiFe(SeO3)3 is built on the 3D anionic framework of ion(III) selenite with the bismuth(III) ions located at its Fe6Se6 12-MR tunnels. Pb3(TeO3)Cl4 (Pna21) is polar and BiFe(SeO3)3 (P212121) is noncentrosymmetric. Powder second-harmonic generation (SHG) measurements using 1064 nm radiation indicate that BiFe(SeO3)3 exhibits a weak SHG efficiency of about 0.2 × KH2PO4 (KDP). Magnetic property measurements for BiFe(SeO3)3 show a dominant antiferromagnetic interaction with weak spin-canting at low temperatures. IR, UV-vis and thermogravimetric, as well as electronic structure calculations were also performed.
Co-reporter:Xiang-Ying Qian, Jian-Han Zhang, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2012 - vol. 41(Issue 4) pp:NaN1236-1236
Publication Date(Web):2011/11/28
DOI:10.1039/C1DT11481F
The first examples of lanthanide(III) organoarsonates, Ln(L1)(H2O)3 (Ln = La (1), H3L1 = 4-hydroxy-3-nitrophenylarsonic acid), Ln(L1)(H2O)2 (Ln = Nd (2), Gd (3)), and mixed-ligand lanthanide(III) organoarsonates, Ln2(HL1)2(C2O4)(H2O)2 (Ln = Nd (4), Sm (5), Eu (6)), were hydrothermally synthesized and structurally characterized. Compounds 1–3 feature a corrugated lanthanide arsonate layer, in which 1D lanthanide arsonate inorganic chains are further interconnected via bridging L13− ligands. Compounds 4–6 exhibit a complicated 3D network. The interconnection of the lanthanide(III) ions by the bridging arsonate ligand leads to the formation of a novel 3D framework with long narrow 1D tunnels along the a-axis, with the oxalate anions are located at the above tunnels and bridging with lanthanide(III) ions. Compounds 2 and 4 exhibit the characteristic emission bands of the Nd(III) ion, whereas compound 6 displays the characteristic emission bands of the Eu(III) ion. The magnetic properties of compounds 3–6 were also investigated.
Co-reporter:Xiang-Ying Qian, Tian-Hua Zhou and Jiang-Gao Mao
Dalton Transactions 2015 - vol. 44(Issue 30) pp:NaN13580-13580
Publication Date(Web):2015/06/18
DOI:10.1039/C5DT01370D
Three new octanuclear Th(IV) arsonates, namely [Th8(O)(L)6(HL)6(H2O)12]·19.5H2O (1) (H3L = o-HO3S–C6H4–AsO3H2), [Th8(O)(L)6(HL)6(H2O)10]·17H2O (2) and [Th8(O)(L)6(HL)6(H2O)5]·0.5H2O (3), with o-sulfophenylarsonic acid as the bridging ligand, have been prepared under hydrothermal conditions. Each complex contains [Th8O13]6+ octanuclear cluster cores composed of two [Th4O6]4+ units bridged by a μ2-oxo anion. The structure of compound 1 features a 0D highly symmetric polynuclear cluster encapsulating the octanuclear core of [Th8O13]6+ which is further decorated by six L3− and six HL2− ligands. Compound 2 features one-dimensional chains along the b-axis in which the neighboring clusters similar to 1 are bridged by a pair of sulfophenylarsonate ligands via M–O–S–O–M bridges. Compound 3 with chiral P212121 features two-dimensional cluster layers, in which each cluster connects with four neighbors via four M–O–S–O–M linkages. Compounds 2 and 3 display unusual broad green light emission bands at 523 nm (λex = 320 nm) and 517 nm (λex = 312 nm), respectively, which originate from the ligand-to-metal charge transfer (LMCT) transition.
Co-reporter:Xue-Li Cao, Fang Kong, Zhang-Zhen He and Jiang-Gao Mao
Dalton Transactions 2015 - vol. 44(Issue 25) pp:NaN11428-11428
Publication Date(Web):2015/05/11
DOI:10.1039/C5DT01257K
Three new transition metal copper(II) selenites or tellurites, namely, CdCu(SeO3)2 (1), HgCu(SeO3)2 (2), and Hg2Cu3(Te3O8)2 (3), have been obtained by conventional hydrothermal reactions of CdO (or Hg2Cl2), CuO and SeO2 (or TeO2). Compounds 1 and 2 are isostructural and crystallize in P21/c. Their structures feature a 3D anionic framework of Cu(SeO3)22− with 1D channels of eight-membered rings (MRs) along the c-axis and a-axis, respectively, which are filled by Cd2+ or Hg2+ cations. Compound 3 crystallizes in a tetragonal system of space group P4212. Its structure is characterized by a [Cu3(Te3O8)2]2− honeycomb layer composed of [Te3O8]4− anions interconnected by Cu2+ ions with 1D channels of 8-MRs along the c-axis. TOPOS analysis indicates that the copper(II) tellurite layer exhibits a new topological structure with a Schläfli symbol of {46·89}2{46}3. The above anionic copper(II) tellurite layers are further linked by dumbbell Hg22+ cations to form a novel 3D framework. Magnetic measurements based on magnetic susceptibility and heat capacity indicate that compounds 1 and 2 show a spin-singlet ground state with a spin gap based on the [Cu2O8]12− dimeric model, whereas compound 3 exhibits a 2D spin-system with an antiferromagnetic ordering around 25 K correlated with its honeycomb [Cu3(Te3O8)2]2− layer. Furthermore, crystalline structures, thermal stabilities, IR spectra and UV-Vis diffuse reflectance spectra have also been studied.
Co-reporter:Dong Yan, Fei-Fei Mao, Ting-Ting Ruan and Jiang-Gao Mao
Dalton Transactions 2017 - vol. 46(Issue 22) pp:NaN7368-7368
Publication Date(Web):2017/05/12
DOI:10.1039/C7DT01360D
Two novel tartratoborates, namely, K2[(C4H2O6)(B3O4H)](H2O) (1) and KCu2[(C4H2O6)2B](H2O)2.5 (2), have been successfully synthesized by solvothermal reactions. They feature different kinds of structural types based on hybrid borate–tartrate motifs. The structure of compound 1 features a 3D network composed of novel [(C4H2O6)2(B3O4H)2]4− anionic groups interconnected by K+ cations. The [(C4H2O6)2(B3O4H)2]4− anion was formed by the condensation of two (B3O8H)6− groups and two tartrate anions, and such condensation reaction has never been reported previously. Compound 2 exhibits a novel 3D network structure in which 2D {Cu2[(C4H2O6)2B](H2O)2}− layers are further interconnected via K+ ions. The [(C4H2O6)2B]5− anion was formed by the condensation of two tartrate anions with a B(OH)4− unit. Magnetic measurements reveal a dominant antiferromagnetic interaction between neighboring Cu2+ ions in compound 2. Furthermore, UV-vis and infrared spectra and thermal analyses were also performed.
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