Co-reporter:Peipei Sun;Shuzhen Liu;Jingyu Han;Yali Shen;Hui Sun
Transition Metal Chemistry 2017 Volume 42( Issue 5) pp:387-393
Publication Date(Web):20 April 2017
DOI:10.1007/s11243-017-0141-0
Four organic–inorganic hybrid selenidostannates, namely [H2en][H2dien][Fe(dien)2]2(Sn2Se6)2 (1), [Fe(dien)2]2Sn2Se6 (2), [Fe(dien)2]FeSnSe4 (3), and [Mn(dien)2]MnSnSe4 (4) (en = ethylenediamine; dien = diethylenetriamine), were prepared in different solvents under solvothermal conditions. Complexes 1 and 2 consist of discrete [Sn2Se6]4− and [Fe(dien)2]2+ ions, as well as organic cations [H2en]2+ and [H2dien]2+ in 1. The dimeric [Sn2Se6]4− anion is formed by two SnSe4 tetrahedra via edge-sharing. Complexes 3 and 4 are composed of one-dimensional polyanions [TMSnSe42−]n plus [TM(dien)2]2+ counter cations (TM = Fe, Mn). In the [TMSnSe42−]n anionic chain, the TM and Sn atoms are located at the same metal site with a ratio of 0.5/0.5. The TM1/2Sn1/2Se4 tetrahedra are interlinked via edge-sharing, forming the heterometallic [TMSnSe42−]n polymeric anion. The [TM(dien)2]2+ cations in 1–2 and 3–4 have u-fac and mer configurations, respectively. In all four crystal structures, the anions and cations are connected into extended structures via weak N–H···Se hydrogen bonds. The band gaps of complexes 1–4 calculated from the solid-state UV–vis diffuse reflectance spectra were at 2.58, 2.60, 2.21, and 2.25 eV, respectively. Thermogravimetric analyses show that complex 1 decomposes in three steps, while complexes 2–4 each decompose in one step.
Co-reporter:SHUZHEN LIU;PEIPEI SUN;JINGYU HAN;YUN LIU;YALI SHEN
Journal of Chemical Sciences 2017 Volume 129( Issue 2) pp:167-175
Publication Date(Web):2017 February
DOI:10.1007/s12039-017-1224-3
New selenidogermanate salts [NH 4] 2[H 2N(CH 3) 2] 2Ge 2Se 6 (1) and [Ni(dien) 2] 2Ge 2Se 5(Se 2) (2) (dien = diethylenetriamine), and a selenidogermanate complex [{Ni(tepa)} 2(μ-Ge 2Se 6)] (3) (tepa = tetraethylenepentamine) were prepared by solvothermal reactions. Compounds 1 and 2 consist of discrete [Ge 2Se 6] 4− and [Ge 2Se 7] 4− anions, and NH\(_{4}^{+}\), [H 2N(CH 3) 2] + and [Ni(dien) 2] 2+ counter cations, respectively. The [Ge 2Se 6] 4− anion is constructed by two tetrahedral GeSe 4 building units via edge-sharing. In 2, two tetrahedral GeSe 4 units are linked by a corner and a Se–Se bond to form a polyselenidogermanate anion [Ge 2Se 7] 4− containing a five-membered ring Ge 2Se 3. The dimeric [Ge 2Se 6] 4− anion acts as a bridging ligand via the trans terminal Se atoms to link two [Ni(tepa)] 2+ cations, resulting in neutral complex 3. The Ni 2+ ion in 2 is coordinated by two tridentate dien ligands, while it is coordinated by a pentadentate tepa ligand and a selenidogermanate anion in 3. The different coordination environments of Ni 2+ ions indicate the influence of the denticity of ethylene polyamines on the formation of selenidogermanates in the presence of transition metal ions. The compounds 1–3 exhibit optical band gaps between 2.06 and 2.35 eV.
Co-reporter:Peipei Sun;Shuzhen Liu;Jingyu Han;Yali Shen
Monatshefte für Chemie - Chemical Monthly 2017 Volume 148( Issue 2) pp:209-216
Publication Date(Web):2017 February
DOI:10.1007/s00706-016-1777-8
New lanthanide(III) compounds [[Ln(tepa)(Cl)]-[Ln(tepa)(OH)]2(SbSe4)2]n (Ln=Sm, Eu), [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2] (Ln=Eu, Gd, Ho) (tepa=tetraethylenepentamine) were prepared by solvothermal methods. Acting as a bidentate μ-1κ:2κ-SbSe4 bridging ligand, the [SbSe4]3− unit interconnects [[Ln(tepa)]2(OH)2]4+ and [Ln(tepa)Cl]2+ (Ln=Sm, Eu) ions to form one-dimensional coordination polymers [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2]n. The [SbSe4]3− unit acts as monodentate ligand to Ln(III) centers in [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2]. The different coordination modes of the [SbSe4]3− units in [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2]n and [H2tepa][[Ln(tepa)(SbSe4)]2(OH)2] are attributed to the size of Ln3+ ions. The bidentate μ-1κ:2κ-SbSe4 bridging ligand in [[Ln(tepa)(Cl)][Ln(tepa)(OH)]2(SbSe4)2]n is observed in the lanthanide complexes of tetraselenidoantimonate ligands for the first time. All compounds exhibit steep band gaps between 2.04 and 2.31 eV at room temperature.
Co-reporter:Pei-pei Sun;Shu-zhen Liu;Ya-li Shen
Journal of Chemical Crystallography 2017 Volume 47( Issue 5) pp:133-139
Publication Date(Web):22 June 2017
DOI:10.1007/s10870-017-0689-8
Two zinc binuclear complexes based on a hexaselenidobistannate bridging ligand, [{Zn(tren)}2(μ-Sn2Se6)] (1) and [{Zn(tepa)}2(μ-Sn2Se6)] (2) were prepared by solvothermal reactions of Zn, Sn, and Se in tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tepa) solvents, respectively. Compound 1 crystallizes in monoclinic space group C2/c, while 2 in tetragonal I41/a. Acting as a bidentate bridging ligand, the bimeric [Sn2Se6]4− anion joins two [Zn(tren]2+ or two [Zn(tepa]2+ units via two trans terminal Se atoms to form the binuclear complexes 1 and 2, respectively. The Zn2+ ion is in a trigonal bipyramidal environment in 1 and in an octahedral environment in 2. Compounds 1 and 2 show well-defined absorption edges with band gaps of 2.38 and 2.31 eV at room temperature.New transition metal complexes base on hexaselenidobistannate ligand, [{Zn(tren)}2(μ-Sn2Se6)] and [{Zn(tepa)}2(μ-Sn2Se6)] were solvothermaly synthesized in tren and tepa (tren = tris(2-aminoethyl)amine, tepa = tetraethylenepentamine) solvents, respectively.
Co-reporter:Jingyu Han, Yun Liu, Chunying Tang, Yali Shen, Jialin Lu, Yong Zhang, Dingxian Jia
Inorganica Chimica Acta 2016 Volume 444() pp:36-42
Publication Date(Web):1 April 2016
DOI:10.1016/j.ica.2016.01.027
•TM–thioarsenate complexes were prepared by solvothermal methods.•Novel 1κ2As1, As2:1κS1-As3S3 and κS1: κS1-AsS3 coordination to TM centers were obtained.•TM–thioarsenate complexes 1–4 exhibit narrow bandgaps in the range of 1.45–1.74 eV.New members of transition metal complexes with thioarsenate ligands, [Co(peha)][Co(As3S3)2] (peha = pentaethylenehexamine) (1), [Co(trien)(AsS3)] (2), [Cr(trien)(AsS3)] (trien = triethylenetetramine) (3) and [Cr(en)2(AsS3)] (en = ethylenediamine) (4) were prepared by solvothermal reactions in polyamines. In 1, two As3S3 units coordinate to a Co2+ ion with both As- and S-donor atoms in the 1κ2As1,As2:1κS1-As3S3 coordination mode to form the novel [Co(As3S3)2]2− anionic cluster, in which CoAs2, CoAs2S2, and CoAs3S2 rings are formed. Another Co2+ ion is coordinated by a hexadentate peha ligand to form a octahedral [Co(peha)]2+ complex cation. Both Co3+ and Cr3+ ions are coordinated by a tetradentate trien ligand and a bidentate chelating ligand [AsS3]3−, and neutral complexes [Co(trien)(AsS3)] (2) and [Cr(trien)(AsS3)] (3) are formed. The Cr3+ is coordinated by two en ligands and a bidentate chelating ligand [AsS3]3− to form neutral complex Cr(en)2(AsS3)] (4). Complexes 2–4 represent the first examples of TM–thioarsenate complexes with polyethyleneamine coligands. Compounds 1–4 are potential semiconductors with narrow well-defined optical band gaps in the range of 1.45–1.74 eV. Thermal properties of 1–4 were investigated via thermogravimetric analyses.New transition metal complexes with thioarsenate ligands were prepared by solvothermal reaction in polyamines, and the first examples of TM-AsS3 complexes with polyethyleneamine coligands were obtained.
Co-reporter:Jingyu Han, Yun Liu, Jialin Lu, Chunying Tang, Fang Wang, Yali Shen, Yong Zhang, Dingxian Jia
Inorganic Chemistry Communications 2015 Volume 57() pp:18-21
Publication Date(Web):July 2015
DOI:10.1016/j.inoche.2015.04.018
•Lanthanide silver thiostannates 1–3 were prepared using solvothermal methods.•The novel [Ag6Sn6S20]10 − cluster is obtained with Ln complex counter cations.•1–3 exhibit optical band gaps between 2.18 and 2.47 eV.Novel organic hybrid silver thiostannates [Hen]4[Ln(en)4]2[Ag6Sn6S20]·3en (Ln = Er, 1; Tm, 2; Yb, 3) were prepared by the reactions of Ln2O3, Ag, Sn and S in ethylenediamine (en) under solvothermal conditions. Six SnS4 tetrahedra and six AgS3 triangles are connected into the heterometallic sulfide cluster [Ag6Sn6S20]10 − via edge-sharing. In the [Ag6Sn6S20]10 − cluster, a hexanuclear Ag6S6 core is enclosed by two Sn3S10 fragments. The Ag6S6 core is the first As–S cluster stabilized by inorganic SnS4 ligands. In 1–3, all Ln3 + ions are in 8-fold coordination environments that involved four bidentate en ligands, forming bicapped trigonal prisms. Compounds 1–3 show well-defined absorption edges with band gaps in the range of 2.18–2.47 eV.Novel silver thiostannates [Hen]4[Ln(en)4]2[Ag6Sn6S20]·3en (Ln = Er, 1; Tm, 2; Yb, 3) were prepared by solvothermal methods. Compounds 1–3 are the first examples of ternary silver-chalcogenidostannates containing Ln complex counter cations.
Co-reporter:Chunying Tang, Yun Liu, Fang Wang, Jialin Lu, Yali Shen, Yong Zhang, Dingxian Jia
Inorganica Chimica Acta 2015 Volume 429() pp:67-72
Publication Date(Web):1 April 2015
DOI:10.1016/j.ica.2014.12.038
•Sm/Sn/S system was firstly investigated in mixed polyamine.•Lanthanide selenidostannates with mixed polyamine ligands were prepared.•The lanthanide selenidostannates exhibit optical bandgaps between 2.18 and 2.41 eV.Samarium selenidostannates [Hen][Sm(dien)3]Sn2Se6 (1), [Sm(trien)(tren)(Cl)]2Sn2Se6·0.5en (2), and [{Sm(en)(trien)}2(μ-OH)2]Sn2Se6 (3) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine, tren = tris(2-aminoethyl)amine) were prepared by solvothermal methods in mixed solvents of en/dien and en/trien, respectively. Compounds 1 and 2 consist of [Sn2Se6]4− anion and mononuclear Sm(III)-complex cations, and/or a protonated en and half a free en molecule. Compound 3 is composed of a [Sn2Se6]4− anion and a binuclear [{Sm(en)(trien)}2(μ-OH)2]4+ complex cation. As far as we know, 1–3 are the first examples of the lanthanide selenidostannates prepared in mixed ethylene polyamines. In the crystal structures of 1–3, the cations and anions are connected into three-dimensional supramolecular networks by N–H⋯Se and/or N–H⋯N, N–H⋯Cl and O–H⋯Se hydrogen bonds. Compounds 1–3 exhibit bandgaps in the range of 2.18–2.41 eV, and a distinct blue-shift of the bandgap from 2 to 1 and 3 is observed.New lanthanide selenidostannates were prepared in mixed ethylene polyamines, and lanthanide complexes with mixed amino ligands were obtanied.
Co-reporter:Fang Wang;Chun-ying Tang;Jia-lin Lu;Ya-li Shen
Journal of Chemical Crystallography 2015 Volume 45( Issue 2) pp:61-66
Publication Date(Web):2015 February
DOI:10.1007/s10870-015-0564-4
Two gadolinium selenidoantimonates [Gd(trien)2]SbSe4 (1) and [Gd(dien)(trien)(SbSe4)] (2) (trien = triethylenetetramine, dien = diethylenetriamine), were prepared by solvothermal reactions of Gd2O3, Sb and Se in trien and mixed trien + dien solvents respectively. Compounds 1 and 2 crystallize in monoclinic space group P21/c and P21/n, respectively. Cell Parameters of 1 are a = 9.2638(17), b = 13.462(3), c = 19.647(4) Å, β = 92.776(3)°, V = 2,447.4(8) Å3, Z = 4. Cell Parameters of 2 are a = 10.210(2), b = 17.602(4), c = 12.377(3) Å, β = 90.280(5)°, V = 2,224.5(9) Å3, Z = 4. In 1 the anion [SbSe4]3− exists as an isolated, charge-compensating anion for the [Gd(trien)2]3+ complex cation. It coordinates to the Gd(III) center of [Gd(dien)(trien)]3+ as a monodentate ligand to form a neutral mixed-coordinate complex [Gd(dien)(trien)(SbSe4)] (2). The coordination to Gd(III) center is influenced by the co-ligands of polyamines.
Co-reporter:Jing-yu Han;Yun Liu;Jia-lin Lu;Chun-ying Tang
Journal of Chemical Crystallography 2015 Volume 45( Issue 7) pp:355-362
Publication Date(Web):2015/07/01
DOI:10.1007/s10870-015-0601-3
New binuclear transition metal complexes concerning the bidentate S-donor ligand μ-Sn2S6, [{Mn(tren)}2(μ-Sn2S6)] (1), [{Zn(tren)}2(μ-Sn2S6)] (2), and [{Mn(tepa)}2(μ-Sn2S6)] (3) [tren = tris(2-aminoethyl)amine, tepa = tetraethylenepentamine] were prepared under methanolothermal conditions. The Mn2+ and Zn2+ ions are coordinated by a tren ligand, forming [TM(tren)]2+ (TM = Mn, Zn) units. As a bidentate bridging ligand, the hexathiobistannate [Sn2S6]4− anion joins two [TM(tren)]2+ units via trans terminal S atoms to form neutral complexes 1 and 2. Both Mn2+ and Zn2+ ions are in a trigonal bipyramidal environment. In 3, the Mn2+ ion binds a pentadentate tepa ligand to give a [Mn(tepa)]2+ unit. Two [Mn(tepa)]2+ units are connected by a μ-Sn2S6 bridging ligand, forming neutral complex [{Mn(tepa)}2(μ-Sn2S6)], in which the Mn2+ ion is in an octahedral environment. Intermolecular N–H···S H-bonding interactions connect 1–3 into layered structures, while 3 forms a three-dimensional network via the N–H···S H-bonds. 1–3 exhibit possible semiconducting properties with the band gaps at 2.3, 2.7 and 2.4 eV, respectively.
Co-reporter:Chunying Tang, Fang Wang, Jialin Lu, Dingxian Jia, Wenqing Jiang, and Yong Zhang
Inorganic Chemistry 2014 Volume 53(Issue 17) pp:9267-9273
Publication Date(Web):August 13, 2014
DOI:10.1021/ic501381v
The novel iron selenidostannates [Fe(bipy)3]Sn4Se9·2H2O (1) and [Fe(bipy)3]2[Sn3Se7]2·bipy·2H2O (2) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl2·4H2O, bipy, and dien with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In 1, four SnSe5 units condense via edge sharing to form the novel 3-D framework selenidostannate ∞3[Sn4Se92–] containing an interpenetrating channel system. The [Fe(bipy)3]2+ cations are accommodated in the different channels according to the conformation of the [Fe(bipy)3]2+ cation. In 2, three SnSe5 units share edges to form a 2-D ∞2[Sn3Se72–] layered anion, while two SnSe5 units and one SnSe4 unit are connected via edge sharing, forming a 1-D ∞1[Sn3Se72–] chainlike anion. The ∞1[Sn3Se72–], [Fe(bipy)3]2+, bipy, and H2O species are embedded between the ∞2[Sn3Se72–] layers. 2 is the first example of a selenidostannate constructed by both ∞2[Sn3Se72–]and ∞1[Sn3Se72–] anions. The coexistence of 1-D ∞1[Sn3Se72–] and 2-D ∞2[Sn3Se72–] anions in 2 might support the possible reaction mechanism that the ∞2[Sn3Se72–] anions are formed by condensation of the ∞1[Sn3Se72–] chains. 1 and 2 exhibit band gaps at 1.43 and 2.01 eV, respectively.
Co-reporter:Chunying Tang, Fang Wang, Dingxian Jia, Wenqing Jiang and Yong Zhang
CrystEngComm 2014 vol. 16(Issue 10) pp:2016-2024
Publication Date(Web):03 Dec 2013
DOI:10.1039/C3CE41759J
Novel heterometallic Ag–iodoplumbates [Ln(DMSO)8]Pb2Ag2I9 [Ln = La(1), Gd(2), Tm(3)] were prepared by reactions of LnCl3, PbI2, AgNO3 and KI in dimethyl sulfoxide (DMSO). The same reactions without reactant AgNO3 produced new iodoplumbates [Ln(DMSO)8][(DMSO)Pb4I11] [Ln = La(4), Pr(5), Nd(6)]. All Ln3+ ions are solvated with eight DMSO molecules in the reactions, forming [Ln(DMSO)8]3+ complex cations to act as counterions to the iodometallate anions. In compounds 1–3, two AgI4 tetrahedra and two PbI6 octahedra are connected into the 1D heterometallic Ag–Pb iodometallate [Ag2Pb2I9]n3n−via face-sharing. The [Ag2Pb2I9]n3n− anionic chains run parallel along the b axis in 1, and along the a axis in 2 and 3. The [Ln(DMSO)8]3+ cations are located between the chains. In compounds 4–6, two PbI6 and two PbI5O octahedra are interlinked end to end via sharing common faces to generate a 1D [(DMSO)Pb4I11]n3n− chain, which represents a new member of iodoplumbate aggregates. In the [(DMSO)Pb4I11]n3n− chain, the Pb2+ ions are joined not only via μ-I bridges, but also via μ-O bridges. The μ-O oxygen bridging has never been observed in iodoplumbates. Solid state optical absorption spectral analyses show optical band gaps in the range of 2.25–2.88 eV for compounds 1–6. Blue shift of the absorption edge caused by copolymerization of the AgI4 unit occurs on the iodoplumbates.
Co-reporter:Yali Shen, Jialin Lu, Chunying Tang, Wang Fang, Dingxian Jia and Yong Zhang
Dalton Transactions 2014 vol. 43(Issue 24) pp:9116-9125
Publication Date(Web):07 Apr 2014
DOI:10.1039/C4DT00358F
Hybrid organic–inorganic Pb–Ag heterometallic iodides [(en)2(PbAgI3)]2n·nH2O (1), [(pda)2(PbAgI3)]n (2), [(tmeda)(PbAgI3)]n (3), [(trien)(PbAgI3)]n (4), [(tepa)(PbAg2I4)]n (5), and [{(dien)3(CO3)}2(Pb6Ag8I15)]nIn (6) were prepared by the reactions of PbI2, AgI (or Ag2CO3) and KI with different polyamines in N,N′-dimethylformamide (DMF) solution. In 1–4, two AgI4 tetrahedra share a common edge to form the bimeric Ag2I6 unit. It coordinates to the Pb(II) ion of [PbL2]2+ or [PbL′]2+ (L = en, pda; L′ = tmeda, trien) via iodine atoms to form hybrid organic–inorganic heterometallic iodides 1, 2, 3 and 4, respectively. Compounds 1, 3, and 4 contain 2-D layered backbones of [PbAgI3]n, whereas 2 contains a backbone of [PbAgI3]n with a 3-D structure. Steric hindrance and denticity of the ethylene polyamines influence the coordination modes and connection strength between the iodoargentate aggregates and Pb(II) ions. In 5, the AgI4 units are joined via sharing common edges to form a 1-D polymeric [Ag2I4]n2n− anion. It is connected with [Pb(tepa)]2+via iodine atoms to form a 3-D network of [(tepa)(PbAg2I4)]n. In 6, the CO32− ion binds three [Pb(dien)]2+ units to form the novel trinuclear [{Pb(dien)}3(μ3-CO3)]4+ complex ion. Eight AgI4 tetrahedra are connected via sharing common edges to give a novel Ag8I15 cluster with C3 symmetry. The Ag8I15 cluster and the [{Pb(dien)}3(CO3)]4+ unit are connected to form a novel layered heterometallic iodometallate cation [{(dien)3(CO3)}2(Pb6Ag8I15)]nn+via sharing iodine atoms. Compounds 1–6 represent a new type of hybrid organic–inorganic heterometallic iodide containing coordinative organic components. Optical absorption spectra show a blue shift of the absorption edges for 1–6 compared with those of the bulk PbI2 and AgI solids.
Co-reporter:Jia-Lin Lu, Chun-Ying Tang, Fang Wang, Ya-Li Shen, Ya-Xian Yuan, Ding-Xian Jia
Inorganic Chemistry Communications 2014 Volume 47() pp:148-151
Publication Date(Web):September 2014
DOI:10.1016/j.inoche.2014.07.037
•Chromium selenidostannates 1 and 2 were firstly prepared using ionothermal methods.•1 and 2 are the first examples of ionothermally synthesized TM-chalcogenidostannates.•The chromium selenidostannates exhibit optical band gaps of 2.08 and 2.19 eV.Ternary chromium selenidostannates [Cr(tepa)(OH)]2Sn2Se6·H2O (tepa = tetraethylenepentamine) (1) and [Cr(peha)]2(Sn2Se6)Cl2 (peha = pentaethylenehexamide) (2) were successfully synthesized by the reaction of CrCl3·6H2O, Sn, Se and tepa or peha in ionic liquid 1-ethyl-3-methylimidazolium chloride at 160 °C. In the ionic liquid, the Cr3 + ion forms [Cr(tepa)(OH)]2 + or [Cr(peha)]3 + chelating complex cations, which lead to the formation of chromium selenidostannates 1 and 2. But the reactions in pure tepa or peha under solvothermal conditions produced amorphous powders. 1 and 2 are the first examples of TM-complex contained chalcogenidostannates synthesized by ionothermal technique. Both 1 and 2 form three-dimensional networks via intermolecular NH⋯Se, OH⋯Se and NH⋯O or NH⋯Cl interactions, respectively. 1 and 2 exhibit possible semiconducting properties with the band gaps at 2.08 and 2.19 eV, respectively.Chromium selenidostannates [Cr(tepa)(OH)]2Sn2Se6·H2O (1) and [Cr(peha)]2(Sn2Se6)Cl2 (2) were firstly prepared under ionothermal conditions. 1 and 2 are the first examples of ionothermally synthesized chalcogenidostannates containing TM-complexes.
Co-reporter:Chunying Tang, Fang Wang, Wenqing Jiang, Yong Zhang, and Dingxian Jia
Inorganic Chemistry 2013 Volume 52(Issue 19) pp:10860-10868
Publication Date(Web):September 24, 2013
DOI:10.1021/ic4007982
Solvothermal reactions of As2O3 and S with CoCl2·6H2O or NiCl2·6H2O in an aqueous solution of dien produced novel thioarsenates [Co(dien)2][Co(As3S3)2] (1) and [Ni(dien)2][Ni(As3S3)2] (2) (dien = diethylenetriamine), and the reaction with CoCl2·6H2O in an aqueous solution of en afforded complex [Hen]2[{Co(en)}6(μ3-S)4(AsS3)4] (3) (en = ethylenediamine). In 1 and 2, one transition-metal ion is coordinated by two dien ligands to form [TM(dien)2]2+ (TM = Co, Ni) complex cations. The As3S3 unit coordinates to the other TM(II) ion with both As- and S-donor atoms to form the [TM(As3S3)2]2– anionic cluster, in which TMAs2, TMAs2S2, and TMAs3S2 rings are formed. In 3, each Co3+ ion is coordinated by an en ligand. Six Co(en) units are interlinked by four μ3-S and four AsS3 ligands to form a [{Co(en)}6(μ3-S)4(AsS3)4]2– cluster containing an adamantane-like Co6S4 core. The AsS3 unit coordinates to Co atom in the η1-As1,η2-S coordination mode with As binding Co(1) and S(1) binding Co(1) and Co(2). The As3S3 and AsS3 ligands with both As- and S-donor atoms in 1–3 have never been obtained in amine solution before. The same reactions in pure dien and en solvents afforded compounds [Co(dien)2]3[As3S6]2 (4) and [Co(en)3]2As2S5 (5) containing discrete anions [As3S6]3– and [As2S5]4–, respectively. The band gaps of 1–3 are in the range of 1.37–1.55 eV, and the band gaps of 4 and 5 are 2.24 and 2.26 eV, which show the influence of the coordination mode of thioarsenate ligands on the electronic transitions in the TM-thioarsenates.
Co-reporter:Wang Fang, Chunying Tang, Ruihong Chen, Dingxian Jia, Wenqing Jiang and Yong Zhang
Dalton Transactions 2013 vol. 42(Issue 42) pp:15150-15158
Publication Date(Web):19 Aug 2013
DOI:10.1039/C3DT51829A
Heterometallic Pb–Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8]3+ complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22]6− anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I319−]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12]6− building block. The [Ag6I12]6− blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I93−]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials.
Co-reporter:Weiwei Tang, Chunying Tang, Fang Wang, Ruihong Chen, Yong Zhang, Dingxian Jia
Journal of Solid State Chemistry 2013 Volume 199() pp:287-294
Publication Date(Web):March 2013
DOI:10.1016/j.jssc.2012.12.035
New heterometallic thioantimonates(III) [Co(dien)2]HgSb2S5 (1), [Ni(dien)2]HgSb2S5 (2) and [H2dien]HgSb8S14 (3), and a mixed-valent thioantimonate(III,V) [Co(dien)2]2Sb4S9 (4) were solvothermally prepared in diethylenetriamine (dien) solvent from Co(Ni)–Hg–Sb–S, Hg–Sb–S and Co–Sb–S systems, respectively. In 1 and 2, the bimeric subunit Sb2S5 condenses with HgS4 tetrahedron via sharing common S atoms to form an one-dimensional [HgSb2S5]n2n− chain, in which a new μ3-1κ2S1,S5:2κS2:3κS4 bridging mode of the Sb2S5 subunit is obtained. In 3, four SbS3 trigonal pyramids and a linear HgS2 unit condense via sharing S atoms to generate an one-dimensional double-lined [HgSb8S14] n2n− chain. In 4, three SbIIIS3 pyramids and a SbVS4 tetrahedron share common corners to form an one-dimensional mixed-valent [Sb4S9]n4n− anion. The syntheses of 1–4 demonstrated that the Hg2+ ion is easily incorporated into thioantimonate networks, and has a higher affinity to S than that of transition metals. 1–4 exhibit semiconducting properties with optical band gaps in 2.0–2.4 eV.Graphical abstarctMercury thioantimonates(III) and thioantimonate(III,V) were solvothermally prepared, and a new coordination mode for the Sb2S5 subunit are observed in the mercury thioantimonates(III). Highlights► Mercury(II)–thioantimonates(III) [Co(dien)2]HgSb2S5, [Ni(dien)2]HgSb2S5 and [H2dien]HgSb8S14 and a a mixed-valent thioantimonate(III,V) [Co(dien)2]2Sb4S9 were solvothermally prepared. ► A new μ3-1κ2S1,S5:2κS2:3κS4 bridging coordination mode of the Sb2S5 subunit is obtained. ► The mercury(II)–thioantimonates(III) are semiconducting materials with band gaps in 2.04–2.25 eV.
Co-reporter:Ruihong Chen;Fang Wang;Chunying Tang;Yong Zhang ;Dr. Dingxian Jia
Chemistry - A European Journal 2013 Volume 19( Issue 25) pp:8199-8206
Publication Date(Web):
DOI:10.1002/chem.201300044
Abstract
Two types of 4f–3d thiostannates with general formula [Hen]2[Ln(en)4(CuSn3S9)]⋅0.5 en (Ln1; Ln=La, 1; Ce, 2) and [Hen]4[Ln(en)4]2[Cu6Sn6S20]⋅3 en (Ln2; Ln=Nd, 3; Gd, 4; Er, 5) were prepared by reactions of Ln2O3, Cu, Sn, and S in ethylenediamine (en) under solvothermal conditions between 160 and 190 °C. However, reactions performed in the range from 120 to 140 °C resulted in crystallization of [Sn2S6]4− compounds and CuS powder. In 1 and 2, three SnS4 tetrahedra and one CuS3 triangle are joined by sharing sulfur atoms to form a novel [CuSn3S9]5− cluster that coordinates to the Ln3+ ion of [Ln(en)4]3+ (Ln=La, Ce) as a monodentate ligand. The [CuSn3S9]5− unit is the first thio-based heterometallic adamantane-like cluster coordinating to a lanthanide center. In 3–5, six SnS4 tetrahedra and six CuS3 triangles are connected by sharing common sulfur atoms to form the ternary [Cu6Sn6S20]10− cluster, in which a Cu6 core is enclosed by two Sn3S10 fragments. The topological structure of the novel Cu6 core can be regarded as two Cu4 tetrahedra joined by a common edge. The Ln3+ ions in Ln1 and Ln2 are in nine- and eightfold coordination, respectively, which leads to the formation of the [CuSn3S9]5− and [Cu6Sn6S20]10− clusters under identical synthetic conditions. The syntheses of Ln1 and Ln2 show the influence of the lanthanide contraction on the quaternary Ln/Cu/Sn/S system in ethylenediamine. Compounds 1–5 exhibit bandgaps in the range of 2.09–2.48 eV depending on the two different types of clusters in the compounds. Compounds 1, 3, and 4 lost their organic components in the temperature range of 110–350 °C by multistep processes.
Co-reporter:Rui-hong Chen;Fang Wang;Chun-ying Tang;Yong Zhang
Journal of Chemical Crystallography 2013 Volume 43( Issue 6) pp:319-324
Publication Date(Web):2013 June
DOI:10.1007/s10870-013-0423-0
Organic hybrid europium hexachalcogenidodistannates [{Eu(en)3}2(μ-OH)2]Sn2S6 (1), [{Eu(en)3}2(μ-OH)2]Sn2Se6 (2), and [Eu(dien)3]2[(Sn2S6)(SH)2] (3) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally synthesized by the reactions of Sn, S (or Se) and Eu2O3 in en and dien solvents, respectively. Compounds 1–3 crystallize in monoclinic space group P21/n. Crystallographic data for 1: a = 10.1158(13), b = 11.3793(14), c = 14.9487(15) Å, β = 98.209(4)°, V = 1703.1(3) Å3, Z = 2. For 2: a = 10.1359(19), b = 11.771(2), c = 15.423(3) Å, β = 99.322(5)°, V = 1815.8(6) Å3, Z = 2. For 3: a = 11.6559(10), b = 15.1677(13), c = 14.1732(13) Å, β = 95.682(2)°, V = 2493.4(4) Å3, Z = 2. The Eu3+ ion forms binuclear tetravalent [{Eu(en)3}2(μ-OH)2]4+ complex cation to act as counter ion to the [Sn2S6]4− and [Sn2Se6]4− anions in 1 and 2. But it is coordinated with three dien ligands to form the mononuclear trivalent [Eu(dien)3]3+ complex cation in 3. The cations and anions are connected into 3-dimensional networks via O–H···S, N–H···S, or N–H···Se hydrogen bonds, respectively.
Co-reporter:Ruihong Chen, Weiwei Tang, Jingjing Liang, Wenqing Jiang, Yong Zhang and Dingxian Jia
Dalton Transactions 2012 vol. 41(Issue 40) pp:12439-12445
Publication Date(Web):16 Aug 2012
DOI:10.1039/C2DT30960B
Solvothermal reactions of elements Ge and Se with Ln2O3 in a pentadentate polyamine, tetraethylenepentamine (tepa), produced novel neutral lanthanide–selenidogermanate polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n (Ln = Eu 1, Gd 2, Dy 3). The reaction with Dy2O3 in ethylenediamine (en) afforded an ionic selenidogermanate [{Dy(en)3}2(μ-OH)2]Ge2Se6 (4). In compounds 1–3, the Ln3+ ions are coordinated by a tepa and two OH− ligands to form binuclear [{Ln(tepa)}2(μ-OH)2]4+ fragments. Two GeSe4 tetrahedra are linked through two Se–Se bonds to form a novel [Ge2Se8]4− unit containing a six-membered Ge2Se4 ring in the chair conformation. The [Ge2Se8]4− unit acts as a bridging ligand via the trans terminal Se atoms to interlink the [{Ln(tepa)}2(μ-OH)2]4+ fragments into one-dimensional polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n. Compounds 1–3 are the first examples of solvothermally prepared lanthanide complexes with a selenidogermanate anion as a ligand. The [Ge2Se6]4− anion in 4 is composed of two GeSe4 tetrahedra sharing a common edge, and is charge compensated by a [{Dy(en)5}2(μ-OH)2]4+ complex cation. The formation of the [Ge2Se8]4− and [Ge2Se6]4− anions and their behavior towards lanthanide ions in 1–4 show the significant influence of ethylene polyamines on the solvothermal synthesis of Ln selenidogermanates.
Co-reporter:Weiwei Tang, Ruihong Chen, Jing Zhao, Wenqing Jiang, Yong Zhang and Dingxian Jia
CrystEngComm 2012 vol. 14(Issue 15) pp:5021-5026
Publication Date(Web):02 May 2012
DOI:10.1039/C2CE25135C
Neutral lanthanide thioantimonate complexes with the formula [Ln(dien)2(μ-η1, η2-SbS4)]n (Ln1) (Ln = Pr 1a, Nd 1b, Sm 1c) and [Ln(dien)2(η2-SbS4)] (Ln2) (Ln = Eu 2a, Dy 2b) have been synthesized by the solvothermal reaction of antimony and sulfur powders with the corresponding lanthanide oxide in diethylenetriamine (dien). In 1a–1c, the tetrathioantimonate SbS43− anion acts as a μ-η1, η2-SbS4 tridentate bridging ligand to interlink [Ln(dien)2]3+ ions into neutral 1D coordination polymers [Ln(dien)2(μ-η1, η2-SbS4)]n, but it coordinates to the Ln3+ ions of [Ln(dien)2]3+ in 2a and 2b as a η2-SbS4 bidentate chelating ligand, leading to neutral complexes [Ln(dien)2(η2-SbS4)]. The Ln3+ ions are in 9-fold and 8-fold coordinations in Ln1 and Ln2 respectively. A systematic investigation of the crystal structures of five complexes as well as two reported compounds revealed that the soft Lewis basic ligand SbS43− coordinates to the larger lanthanide ions La3+, Ce3+, Pr3+, Nd3+, and Sm3+ as a μ-η1, η2-SbS4 tridentate bridging ligand, and to the smaller lanthanide ions Eu3+ and Dy3+ as a η2-SbS4 bidentate chelating ligand, which exhibits a lanthanide contraction effect on the coordination mode of the SbS43− ligand to the Ln3+ centers.
Co-reporter:Weiwei Tang;Ruihong Chen;Wenqing Jiang;Yong Zhang ;Dingxian Jia
European Journal of Inorganic Chemistry 2012 Volume 2012( Issue 30) pp:4907-4913
Publication Date(Web):
DOI:10.1002/ejic.201200649
Abstract
Novel lanthanide selenidostannate polymers containing the soft-base Sn2Se6 ligand, (H3O)n[La(tepa)(μ-1κ2:2κ2-Sn2Se6)]n (1), [{Nd(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)]n (2), and [{Gd(tepa)(μ-OH)}2(μ-1κ:2κ-Sn2Se6)]n·nH2O (3) (tepa = tetraethylenepentamine) were prepared by treating lanthanide oxides with Sn and Se using pentadentate polyamine tepa as a second ligand under solvothermal conditions. In 1, the La3+ ion is coordinated by a tepa ligand to form an unsaturated [La(tepa)]3+ unit, and the [Sn2Se6]4– anion acts as a tetradentate bridging ligand with four terminal Se atoms to connect the [La(tepa)]3+ units into a coordination polymeric anion [La(tepa)(μ-1κ2:2κ2-Sn2Se6)–]n. The μ-1κ2Se1,Se2:2κ2Se5,Se6 bridging mode in 1 is a new coordination mode for the Sn2Se6 unit to LnIII centers. In 2 and 3, the lanthanide ion is coordinated by a tepa ligand, and two [Ln(tepa)]3+ (Ln = Nd, Gd) ions are joined by two μ-OH bridges to form dinuclear cations. Behaving as a bidentate μ-Sn2Se6 ligand with the trans-terminal Se atoms, the Sn2Se6 units connect the [{Ln(tepa)(μ-OH)}2]4+ cations into neutral coordination polymers [{Ln(tepa)(μ-OH)}2(μ-Sn2Se6)]n. The coordination modes μ-1κ2Se1,Se2:2κ2Se5,Se6 in 1 and μ-1κSe1:2κSe5 in 2 and 3 are related to the metal size of the lanthanide(III) ions. In addition, as an ethylenepolyamine with higher denticity, the pentadentate tepa exhibits a significantly different influence on the structures of the solvothermally synthesized Ln selenidostannates compared to the bidentate ethylenediamine and tridentate diethylenetriamine. Compounds 1–3 are semiconductors with well-defined band gaps of 1.95–2.34 eV.
Co-reporter:Jing Zhao;Wei-wei Tang;Jing-jing Liang;Yong Zhang
Journal of Chemical Crystallography 2012 Volume 42( Issue 3) pp:187-191
Publication Date(Web):2012 March
DOI:10.1007/s10870-011-0222-4
Mix-coordinated praseodymium(III) complexes concerning the [SbSe4]3− inorganic ligand, [Pr(en)2(dien)(η2-SbSe4)] (1) and [Pr(en)(trien)(μ-η1,η2-SbSe4)]n (2) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine), were prepared by solvothermal reactions of Pr2O3, Sb and Se in en + dien and en + trien mixed solvents, respectively. They crystallize in the monoclinic space group P21/n but with different molecular structures. Crystallographic data for 1: a = 8.610(2), b = 27.722(7), c = 9.294(2) Å, β = 108.987(3)°, V = 2097.7(9) Å3, Z = 4. For 2: a = 14.2987(17), b = 9.0176(9), c = 15.4357(18) Å, β = 100.708(3)°, V = 1955.6(4) Å3, Z = 4. The [SbSe4]3− anion coordinates to the Pr3+ ion in [Pr(en)2(dien)]3+ as a η2-SbSe4 chelating ligand, yielding complex 1. It acts as a μ-η1,η2-SbSe4 bridging ligand to connect the [Pr(en)(trien)]3+ ions into the polymer 2. The coordination difference between 1 and 2 is attributed to the coligands of mixed polyamines.
Co-reporter:Jing Zhao ; Jingjing Liang ; Jiangfang Chen ; Yingli Pan ; Yong Zhang ;Dingxian Jia
Inorganic Chemistry 2011 Volume 50(Issue 6) pp:2288-2293
Publication Date(Web):February 20, 2011
DOI:10.1021/ic1024444
Novel cobalt polyselenidoarsenate [Co(phen)3][As2Se2(μ-Se3)(μ-Se5)] (1; phen = 1,10-phenanthroline) was methanolothermally synthesized by the reaction of CoCl2, As2O3, and Se templated by phen in a CH3OH solvent at 130 °C. The same reaction in a H2O solvent yielded cobalt selenidoarsenate [Co(phen)3]2[As8Se14] (2). In 1, the AsSe+ units are alternately joined by the μ-Se32− and μ-Se52− bridging ligands to form a novel helical polyselenidoarsenate chain [As2Se2(μ-Se3)(μ-Se5)2−]∞. In 2, eight pyramidal AsSe3 units are connected via corner sharing into the new member of the selenidoarsenate aggregate [As8Se14]4− with a condensation grade of 0.571, which represents the first discrete selenidoarsenate(III) with a condensation grade of above 0.50. The octahedral complex [Co(phen)3]2+ is formed in situ to act as a countercation in compounds 1 and 2. 1 and 2 exhibit steep absorption band gaps at 2.09 and 2.16 eV, respectively.
Co-reporter:Dingxian Jia, Jing Zhao, Yingli Pan, Weiwei Tang, Bing Wu, and Yong Zhang
Inorganic Chemistry 2011 Volume 50(Issue 15) pp:7195-7201
Publication Date(Web):July 6, 2011
DOI:10.1021/ic2007809
The polyselenidoarsenates [Fe(phen)3][As2Se6] (1), [Zn(phen)(dien)][As2Se6]·2phen (2), [{Mn(phen)2}2(μ–η2,η2-AsSe4)]2[As2Se6]·H2O (3), and [Ni(phen)3][As2Se2(μ-Se3)(μ-Se5)] (4) (dien = diethylenetriamine and phen = 1,10-phenanthroline) were prepared by the reaction of As2O3, Se, dien, and phen in the presence of transition metals in a methanol solvent under solvothermal conditions. Compounds 1–3 consist of [As2Se6]2– anions with [Fe(phen)3]2+, [Zn(phen)(dien)]2+, and [{Mn(phen)2}2(μ-η2,η2-AsSe4)]+ complex counter cations, respectively. The [As2Se6]2– anion is formed from two AsIIISe3 trigonal pyramids linked through two Se–Se bonds. Compound 3 is the first example of a mixed-valent selenidoarsenate(III,V) and exhibits the coexistence of AsIIISe3 trigonal pyramidal and AsVSe4 tetrahedral units. Compound 4 is composed of a helical chain of [As2Se2(μ-Se3)(μ-Se5)2–]∞ and octahedral [Ni(phen)3]2+ cations. The [As2Se2(μ-Se3)(μ-Se5)2–]∞ chain is constructed from AsSe+ units alternatively linked by μ-Se32– and μ-Se52– bridging ligands. When the structures of compounds 1–4 are compared, the transition metal ions show different structural directing effects during the synthesis of arsenic polyselenides in methanol. Compounds 1, 2, 3, and 4 exhibit semiconducting properties with band gaps of 1.88, 2.29, 1.82, and 2.01 eV, respectively.
Co-reporter:Jingjing Liang, Jiangfang Chen, Jing Zhao, Yingli Pan, Yong Zhang and Dingxian Jia
Dalton Transactions 2011 vol. 40(Issue 11) pp:2631-2637
Publication Date(Web):04 Feb 2011
DOI:10.1039/C0DT01424A
Two systems, Ln/Sn/Se/en and Ln/Sn/Se/dien, were investigated under solvothermal conditions, and novel lanthanide selenidostannates [{Ce(en)4}2(μ-Se2)]Sn2Se6 (1a), [{Ln(en)3}2(μ-OH)2]Sn2Se6 (Ln = Pr(1b), Nd(1c), Gd(1d); en = ethylenediamine), [{Ln(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞ (Ln = Ce(2a), Nd(2b)), and [Hdien][Gd(dien)2(μ-SnSe4)] (2c) (dien = diethylenetriamine) were prepared and characterized. Two structural types of lanthanide selenidostannates were obtained across the lanthanide series in both systems. In the Ln/Sn/Se/en system, two types of binuclear lanthanide complex cations [Ce2(en)8(μ-Se2)]4+ and [{Ln(en)3}2(μ-OH)2]4+ (Ln = Pr, Nd, Gd) were formed depending on the Ln3+ ions. The complex cations are compensated by the [Sn2Se6]4− anions. In the Ln/Sn/Se/dien system, coordination polymer [{Ln(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞ and ionic complex [Hdien][Gd(dien)2(μ-SnSe4)] are obtained along the lanthanide series, among which the μ4-Sn2Se9, μ-Sn2Se6 and μ-SnSe4 ligands to the Ln3+ ions were observed. The formation of title complexes shows the effects of lanthanide metal size and amino ligand denticity on the lanthanide selenidostannates. Complexes 1a-2c exhibit semiconducting properties with band gaps between 2.08 and 2.48 eV.
Co-reporter:Jing-Jing Liang, Jing Zhao, Wei-Wei Tang, Yong Zhang, Ding-Xian Jia
Inorganic Chemistry Communications 2011 Volume 14(Issue 6) pp:1023-1026
Publication Date(Web):June 2011
DOI:10.1016/j.inoche.2011.03.062
Novel nickle thiogermanates [Ni(trien)2]2Ge4S10 (1) (trien = triethylenetetramine) and [{Ni(tepa)}2(μ-Ge2S6)] (2) (tepa = tetraethylenepentamine) were respectively synthesized by the reaction of NiCl2·6H2O, GeO2 and S in trien and tepa under solvothermal conditions. The adamantane-like [Ge4S10]4− anion in 1 is composed of four GeS4 tetrahedra sharing the corners with three other tetrahedra via S2− bridges. 1 is the first example of damantane-like [Ge4S10]4− anion with transition metal complex as the counter cation. The bimeric [Ge2S6]4− anion in 2 is constructed by two GeS4 tetrahedra sharing a common edge. It acts as a μ-Ge2S6 ligand with the trans terminal S atoms to connect two [Ni(tepa)]2+ cations into the neutral complex 2. The syntheses of 1 and 2 show the influence of different ethylene polyamines on the formation of thiogermanates in the presence of transition metal. 1 and 2 exhibit semiconducting properties with the band gap Eg at 2.31 and 2.48 eV respectively.Novel nickle thiogermanates [Ni(trien)2]2Ge4S10 and [{Ni(tepa)}2(μ-Ge2S6)] were solvothermally prepared with coordinative amines trien and tepa as templates. The syntheses of two compounds show the different structure-directing effects of ethylene polyamines on the formatin of thiogermanates in the presence of transition metal under solvothermal conditions.Research highlights► New nickle thiogermanates [Ni(trien)2]2Ge4S10 (1) and [{Ni(tepa)}2(μ-Ge2S6)] (2) were prepared. ► Templates trien and tepa exhibit different structural directing effects. ► 1 presents the first example of damantane-like [Ge4S10]4– anion with transition metal counter cation.
Co-reporter:Jing Zhao;Jingjing Liang;Yingli Pan
Monatshefte für Chemie - Chemical Monthly 2011 Volume 142( Issue 12) pp:1203-1209
Publication Date(Web):2011 December
DOI:10.1007/s00706-011-0561-z
New polyselenidoarsenates [Co(dien)2]As2Se6, [Ni(dien)2]As2Se6 (dien = diethylenetriamine), and [Mn(dap)3]As2Se6 (dap = 1,2-diaminopropane) were synthesized by the reaction of As2O3, Se, and transition metal chloride in dien or dap solvent under solvothermal conditions. The compounds consist of a polyselenidoarsenate anion [As2Se6]2− and an octahedral complex cation [M(dien)2]2+ (M = Co, Ni) or [Mn(dap)3]2+. Two trigonal–pyramidal AsSe3 units are joined through two Se–Se bonds forming the dimeric [As2Se6]2− anion with a six-membered ring As2Se4 in chair conformation. In the crystal structures the anion and cations are connected into extended structures via weak N–H···Se hydrogen bonds. Thermogravimetric analyses show that the dien-containing compounds decompose in one step under nitrogen stream, whereas the Mn compound exhibits a two-step decomposition process.
Co-reporter:Jiao Wang, Yingli Pan, Jiangfang Chen, Jiansheng Gu, Yong Zhang and Dingxian Jia
Dalton Transactions 2010 vol. 39(Issue 30) pp:7066-7072
Publication Date(Web):24 Jun 2010
DOI:10.1039/C0DT00040J
Three solvothermal systems Ln/As/Se/en, Ln/As/Se/dien and Ln/As/Se/(en+trien) (Ln = lanthanide excluding Pm, en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine) were investigated in detail across the lanthanide series, and ternary lanthanide selenidoarsenates [Ln(en)3(H2O)(μ-η1,η1-AsSe4)] (Ln = La(1a), Ce(1b), Nd(1c)), [Ln(en)4]AsSe4·0.5en (Ln = Sm(1d), Gd(1e), Dy(1f)), [Ln(dien)2(μ-η1,η2-AsSe4)] (Ln = La(2a), Ce(2b), Pr(2c)), [Ln(en)(trien)(μ-η1,η2-AsSe4)] (Ln = La(3a), Nd(3b)) and [Sm(en)(trien)(η2-AsSe4)] (3c) were prepared. Systematic investigations of the three systems clarify the relationship between the molecular structures of the synthetic lanthanide selenidoarsenates and the metal size evolution of the lanthanide series. Meanwhile, the coordination modes of the [AsSe4]3− tetrahedral anion to the same lanthanide ion are dependent on the denticity of ethylene polyamine as the second ligand. The lanthanide selenidoarsenates exhibit semiconducting properties with Eg between 2.15 and 2.31 eV.
Co-reporter:Ying-Li Pan, Jiang-Fang Chen, Jiao Wang, Yong Zhang, Ding-Xian Jia
Inorganic Chemistry Communications 2010 Volume 13(Issue 12) pp:1569-1571
Publication Date(Web):December 2010
DOI:10.1016/j.inoche.2010.09.014
Two novel inorganic-organic hybrid lanthanide thioantimonates [Ln(dien)2(μ-η1,η2-SbS4)]∞ (Ln = La(1), Ce(2)) were synthesized by reaction of LaCl3 (or CeCl3), Sb and S in dien (dien = diethylenetriamine) under solvothermal conditions. In 1 and 2, the [SbS4]3− anions act as tridentate μ-η1,η2-SbS4 bridging ligands to connect [Ln(dien)2]3+ cations into one-dimensional neutral coordination polymers [Ln(dien)2(μ-η1,η2-SbS4)]∞, in which a new coordination mode of μ-η1,η2-SbS4 is observed for the [SbS4]3− ligand. The Ln3+ ions lie in nine-coordinated polyhedra of LnN6S3, which can be described as distorted monocapped square antiprisms. The syntheses of 1 and 2 show that the soft base S-donor [SbS4]3− ligand can coordinate to hard Lewis acidic lanthanide metals in the presence of amino chelating ligands of dien. The lanthanide selenidoarsenates 1 and 2 exhibit semiconducting properties with Eg between 3.81 and 2.57 eV.Novel inorganic-organic hybrid chalcogenide-based lanthanide complexes [Ln(dien)2(μ-η1,η2-SbS4)]∞ (Ln = La, Ce) were synthesized under solvothermal conditions. The S-donor soft base [SbS4]3− ligand achieves coordination to hard Lewis acidic lanthanide metals with a new coordination mode of μ-η1,η2-SbS4 in the presence of amino chelating ligands of dien.
Co-reporter:Jing-jing Liang;Jing Zhao;Qin-yan Jin
Journal of Chemical Crystallography 2010 Volume 40( Issue 11) pp:975-980
Publication Date(Web):2010 November
DOI:10.1007/s10870-010-9774-y
Two rare earth metal thioantimonates [RE(en)4]SbS4·0.5en (RE = Y(1), Tm(2); en = ethylenediamine) were synthesized under mild solvothermal conditions. Compounds 1 and 2 are isostructural, and both crystallize in monoclinic space group P21/n. Crystallographic data for 1: a = 11.0894(19), b = 12.905(2), c = 16.000(3) Å, β = 91.792(4), V = 2288.7(7) Å3, Z = 4. For 2: a = 11.0870(14), b = 12.8977(16), c = 15.986(2) Å, β = 91.879(3), V = 2284.7(5) Å3, Z = 4. The four-en coordinated rare earth complex cation [RE(en)4]3+ formed in situ balances the charge of the [SbS4]3− anion in the crystal structure. The RE3+ ion is in an eight-coordinated environment involving eight N atoms of four en ligands forming a bicapped trigonal prism. Hydrogen bonds link [RE(en)4]3+, [SbS4]3− and en species into a three-dimensional structure. The structure determination of 1 and 2 implies that the ionic radii of rare earth metal ions play an important role on the structures of the rare earth metal thioantimonates.
Co-reporter:Yingli Pan, Qinyan Jin, Jiangfang Chen, Yong Zhang and Dingxian Jia
Inorganic Chemistry 2009 Volume 48(Issue 12) pp:5412-5417
Publication Date(Web):April 28, 2009
DOI:10.1021/ic9003615
Novel hydrogen-bonded supramolecular thioarsenates [Fe(phen)3][As3S6]·dien·7H2O (1) and [Mn2(phen)4(As2S5)]·phen·2H2O (2) (dien = diethylenetriamine, phen = 1,10-phenanthroline) were hydrothermally synthesized and characterized. The structure of 1 consists of [As3S6]3−−H2O anionic layers and [Fe(phen)3]3+−dien cationic layers assembled via O−H···S and O−H···N hydrogen-bonding interactions. The layers stack alternately and are parallel to each other to give a 3D network structure with channels accommodating unique branched water chains, which are anchored on the anionic and cationic layers via hydrogen bonds. In 2, the [As2S5]4− anion acts as a tetradentate brigding ligand via four terminal S atoms to link two [Mn(phen)2]2+ cations, forming the neutral complex [Mn2(phen)4(As2S5)]. This is a new coordination mode for the [As2S5]4− ion. [Mn2(phen)4(As2S5)], phen, and H2O form a 3D network structure via O−H···S, O−H···O, and π−π stacking interactions.
Co-reporter:Dingxian Jia ; Qinyan Jin ; Jiangfang Chen ; Yingli Pan ;Yong Zhang
Inorganic Chemistry 2009 Volume 48(Issue 17) pp:8286-8293
Publication Date(Web):August 7, 2009
DOI:10.1021/ic900901t
The solvothermal synthetic system Ln/Sb/Se (Ln = La, Eu) was investigated in different ethylene polyamines, and a series of lanthanum and europium selenidoantimonates [La(en)2(dien)(η2-SbSe4)] (Ia), [La(dien)2(μ-η1,η2-SbSe4)] (Ib), [La(trien)2(H2O)]SbSe4 (Ic), [La(en)(trien)(μ-η1,η2-SbSe4)] (Id), [Eu(en)2(dien)(SbSe4)] (IIa), [Eu(en)(trien)(η2-SbSe4)] (IIb), and [Eu(dien)2(η2-SbSe4)] (IIc) (en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine) were prepared. A systematic investigation of the crystal structures showed that the soft Lewis basic ligand [SbSe4]3− can be tuned to coordinate to the hard Lewis acidic lanthanide ions as a monodentate ligand, mono-SbSe4; a bidentate chelating ligand, η2-SbSe4; or a tridentate bridging ligand, μ-η1,η2-SbSe4, by the ethylene polyamines or mixed ethylene polyamines used in the syntheses. The [SbSe4]3− anion exhibited different coordination modes for La3+ and Eu3+ ions in the presence of the same ethylene polyamine because of the different coordination numbers of La3+ and Eu3+ ions.
Co-reporter:Ai-Mei Zhu;Qin-Yan Jin, ;Jian-Sheng Gu ;Yong Zhang
European Journal of Inorganic Chemistry 2008 Volume 2008( Issue 30) pp:4756-4761
Publication Date(Web):
DOI:10.1002/ejic.200800577
Abstract
New lanthanoid selenidostannates [Hdien][Ln(dien)2(μ-SnSe4)] [Ln = Sm (1), Eu (2); dien = diethylenetriamine] were solvothermally prepared by reaction of Ln2O3 (Ln = Sm, Eu) with Sn and Se in dien. The structures of 1 and 2 consist of the tetraselenidostannate anion [SnSe4]4– coordinating to a [Ln(dien)2]3+ fragment as a bidentate chelating ligand. The reaction of Ln2O3 and Se with SnCl4·5H2O under the same solvothermal conditions produces the selenidostannate [Eu2(dien)4(μ-OH)2]Sn2Se6 (3), which is constructed from the two dinuclear ions [Eu2(dien)4(μ-OH)2]4+ and [Sn2Se6]4–. The water molecule prevents the [SnSe4]4– anion from coordinating to the lanthanide center. As far as we know, compounds 1 and 2 are the first selenidostannates integrated within lanthanoid complexes prepared under mild solvothermal conditions. Upon heating, compounds 1 and 2 decompose in three steps, whereas compound 3 undergoes a one-step decomposition procedure. The band gaps of 2.52, 2.08, and 2.43 eV were derived from optical absorption spectra for compounds 1, 2, and 3, respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
Co-reporter:Dingxian Jia, Aimei Zhu, Qinyan Jin, Yong Zhang, Wenqing Jiang
Journal of Solid State Chemistry 2008 Volume 181(Issue 9) pp:2370-2377
Publication Date(Web):September 2008
DOI:10.1016/j.jssc.2008.05.040
Two types of lanthanide selenidoantimonates [Ln(en)4(SbSe4)] (Ln=Ce(1a), Pr(1b)) and [Ln(en)4]SbSe4·0.5en (Ln=Eu(2a), Gd(2b), Er(2c), Tm(2d), Yb(2e); en=ethylenediamine) were solvothermally synthesized by reactions of LnCl3, Sb and Se with the stoichiometric ratio in en solvent at 140 °C. The four-en coordinated lanthanide complex cation [Ln(en)4]3+ formed in situ balances the charge of SbSe43− anion. In compounds 1a and 1b, the SbSe43− anion act as a monodentate ligand to coordinate complex [Ln(en)4]3+ and the neutral compound [Ln(en)4(SbSe4)] is formed. The Ln3+ ion has a nine-coordinated environment involving eight N atoms and one Se atom forming a distorted monocapped square antiprism. In 2a–2e the lanthanide(III) ion exists as isolated complex [Ln(en)4]3+, in which the Ln3+ ion is in a bicapped trigonal prism geometry. A systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series. TG curves show that compounds 1a–1b and 2a–2e remove their organic components in one and two steps, respectively.Two types of lanthanide selenidoantimonates [Ln(en)4(SbSe4)] (Ln=Ce, Pr) and [Ln(en)4]SbSe4·0.5en (Ln=Eu, Gd, Er, Tm, Yb; en=ethylenediamine) have been synthesized under the mild solvothermal conditions, and a systematic investigation of the crystal structures reveals that two types of structural features of these lanthanide selenidoantimonates are related with lanthanides contraction across the lanthanide series.
Co-reporter:Dingxian Jia, Aimei Zhu, Jie Deng, Yong Zhang and Jie Dai
Dalton Transactions 2007 (Issue 20) pp:2083-2086
Publication Date(Web):16 Apr 2007
DOI:10.1039/B701995E
Two novel lanthanide selenidoarsenates(V) [Ln(dien)2(µ3-AsSe4)] (Ln = Nd 1, Sm 2, dien = diethylenetriamine) were synthesized by the reactions of As2O3 and Se with Nd2O3 or Sm2O3 in dien under solvothermal conditions. 1 and 2 are in the orthorhombic crystal system with Iba2 and Pbca space groups, respectively. The [AsSe4]3− anion acts as a tridentate µ3-AsSe4 ligand to bridge the lanthanide [Ln(dien)2]3+ complexes leading to one-dimensional neutral [Ln(dien)2(µ3-AsSe4)]∞ chains. The chains contact through hydrogen bonding to form network structures. The lanthanide center lies within a nine-coordinated environment involving six N atoms of two dien ligands and three Se atoms of two different tetrahedral [AsSe4]3− anions forming a distorted monocapped square antiprism. The novel coordination polymers [Nd(dien)2(µ3-AsSe4)]∞ and [Sm(dien)2(µ3-AsSe4)]∞ are the first examples of solvothermally synthesized selenidoarsenates with [AsSe4]3− anion acting as a ligand in lanthanide complexes. The band gaps of 2.11 eV for 1, and 2.18 eV for 2 have been derived from optical absorption spectra. TG-DSC curves show that two compounds remove coordinated dien ligands in a single step.
Co-reporter:Qianxin Zhao, Dingxian Jia, Yong Zhang, Lifeng Song, Jie Dai
Inorganica Chimica Acta 2007 Volume 360(Issue 6) pp:1895-1901
Publication Date(Web):20 April 2007
DOI:10.1016/j.ica.2006.09.023
Three new lanthanide thiostannates [Ln2(en)6(μ2-OH)2]Sn2S6 (Ln = Nd (1), Gd (2); en = ethylenediamine) and [Gd(dien)3]2[(Sn2S6)Cl2] (3) (dien = diethylenetriamine) were first synthesized by treating LnCl3 with SnCl4 and S under mild solvothermal conditions. Compounds 1 and 2 are isostructural. They consist of a binuclear lanthanide(III) complex [Ln2(en)6(μ2-OH)2]4+ cation and a dimeric [Sn2S6]4− anion. The anion is built up by two SnS4 tetrahedra sharing a common edge. The Nd3+ and Gd3+ ions are in an eight-coordinated environment forming distorted bicapped trigonal prisms. Compound 3 is composed of two monouclear [Gd(dien)3]3+ complex cations, a [Sn2S6]4− anion, and two chlorine ions. The Gd3+ ion has a nine-coordinated environment forming a distorted tricapped trigonal prism. In compounds 1–3, extensive hydrogen bonds are formed leading to three-dimensional networks of anions and cations. The band gaps of 2.42 eV for 1 and 3.17 eV for 2 have been derived from optical absorption spectra. The new lanthanide compounds might be the precursors for ternary lanthanide thiostannates by the heat treatment under nitrogen atmosphere to get rid of organic components.Three new lanthanide thiostannates [Nd2(en)6(μ2-OH)2]Sn2S6, [Gd2(en)6(μ2-OH)2]Sn2S6 and [Gd(dien)3]2[(Sn2S6)Cl2] (where, en = ethylenediamine; dien = diethylenetriamine) have been first synthesized by the solvothermal method with the reaction of SnCl4, S with NdCl3 and GdCl3, respectively. Their crystal structures, optical properties and thermal decomposition are reported.
Co-reporter:Dingxian Jia;Aimei Zhu;Yong Zhang;Jie Deng
Monatshefte für Chemie - Chemical Monthly 2007 Volume 138( Issue 3) pp:191-197
Publication Date(Web):2007 March
DOI:10.1007/s00706-007-0596-3
New selenidogermanates [Mn(en)3]2Ge2Se6 (en = ethylenediamine) and [Fe(dien)2]2Ge2Se6 (dien= diethylenetriamine) were synthesized by the reaction of germanium dioxide, elemental selenium, and transition metal chlorides in respectively en and dien. Both compounds crystallize in the monoclinic space group P21/n with two formula units in the unit cell, and consist of discrete [Ge2Se6]4− anions with transition metal complex cations as counter ions. The [Ge2Se6]4− anion is formed by two GeSe4 tetrahedra sharing a common edge to form a planar Ge2Se2 four-membered ring. The [Mn(en)3]2+ and [Ni(dien)2]2+ complex cations are in distorted octahedral geometry. In both selenidogermanates extensive N–H···Se hydrogen bonding contacts lead to 3-dimensional network structures. The band gaps of 2.36 and 2.25 eV were derived from optical absorption spectra. Thermogravimetric analysis shows that the first compound decomposes in two steps under the nitrogen stream, while the second exhibits a one-step decomposition process.
Co-reporter:Ding-Xian Jia;Qian-Xin Zhao;Yong Zhang;Jie Dai;Jian Zhou
European Journal of Inorganic Chemistry 2006 Volume 2006(Issue 14) pp:
Publication Date(Web):3 MAY 2006
DOI:10.1002/ejic.200600155
Three new lanthanide selenidoantimonates [Ln(en)4(SbSe4)] [Ln = La (1), Nd (2)] and [Sm(en)4]SbSe4·0.5en (3) (en = ethylenediamine) were first synthesized by treating LnCl3, Sb, and Se in a stoichiometric ratio with en under mild solvothermal conditions. Compounds 1 and 2 are isostructural. The Ln3+ ion has a nine-coordinate environment involving eight N atoms from four en ligands and one Se atom from the SbSe43– anion forming a distorted bicapped pentagonal bipyramid. [La(en)4(SbSe4)] and [Nd(en)4(SbSe4)] are the first examples of solvothermally synthesized selenidoantimonates with an SbSe43– anion acting as a ligand in a lanthanide complex. The crystal structure of 3 contains an isolated bicapped trigonal-prismatic coordinated [Sm(en)4]3+ cation, a tetrahedral SbSe43– anion, and half a free en molecule in its asymmetric unit. The bandgaps of 2.22 eV for 1, 2.33 eV for 2, and 2.54 eV for 3 have been derived from optical absorption spectra. Compound 1 loses the en ligands in one step, whereas compound 2 loses them in two steps. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
Co-reporter:Jiang-Fang Chen, Qin-Yan Jin, Ying-Li Pan, Yong Zhang and Ding-Xian Jia
Chemical Communications 2009(Issue 46) pp:NaN7214-7214
Publication Date(Web):2009/10/21
DOI:10.1039/B914603B
Solvothermal reaction of La2O3, Sn and Se in dien yields a novel lanthanide selenidostannate [{La(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞, the first example of the coordination of Sn2Se9 and Sn2Se6 ligands to hard Lewis acidic lanthanide metals, while the reaction in en yields an ionic compound [La2(en)8(μ-Se2)]Sn2Se6 containing a ten-coordinated binuclear lanthanum complex [La2(en)8(Se2)]4+ with the diselenide Se22−group as a bridging ligand.
Co-reporter:Dingxian Jia, Aimei Zhu, Jie Deng, Yong Zhang and Jie Dai
Dalton Transactions 2007(Issue 20) pp:NaN2086-2086
Publication Date(Web):2007/04/16
DOI:10.1039/B701995E
Two novel lanthanide selenidoarsenates(V) [Ln(dien)2(µ3-AsSe4)] (Ln = Nd 1, Sm 2, dien = diethylenetriamine) were synthesized by the reactions of As2O3 and Se with Nd2O3 or Sm2O3 in dien under solvothermal conditions. 1 and 2 are in the orthorhombic crystal system with Iba2 and Pbca space groups, respectively. The [AsSe4]3− anion acts as a tridentate µ3-AsSe4 ligand to bridge the lanthanide [Ln(dien)2]3+ complexes leading to one-dimensional neutral [Ln(dien)2(µ3-AsSe4)]∞ chains. The chains contact through hydrogen bonding to form network structures. The lanthanide center lies within a nine-coordinated environment involving six N atoms of two dien ligands and three Se atoms of two different tetrahedral [AsSe4]3− anions forming a distorted monocapped square antiprism. The novel coordination polymers [Nd(dien)2(µ3-AsSe4)]∞ and [Sm(dien)2(µ3-AsSe4)]∞ are the first examples of solvothermally synthesized selenidoarsenates with [AsSe4]3− anion acting as a ligand in lanthanide complexes. The band gaps of 2.11 eV for 1, and 2.18 eV for 2 have been derived from optical absorption spectra. TG-DSC curves show that two compounds remove coordinated dien ligands in a single step.
Co-reporter:Jiao Wang, Yingli Pan, Jiangfang Chen, Jiansheng Gu, Yong Zhang and Dingxian Jia
Dalton Transactions 2010 - vol. 39(Issue 30) pp:NaN7072-7072
Publication Date(Web):2010/06/24
DOI:10.1039/C0DT00040J
Three solvothermal systems Ln/As/Se/en, Ln/As/Se/dien and Ln/As/Se/(en+trien) (Ln = lanthanide excluding Pm, en = ethylenediamine, dien = diethylenetriamine, trien = triethylenetetramine) were investigated in detail across the lanthanide series, and ternary lanthanide selenidoarsenates [Ln(en)3(H2O)(μ-η1,η1-AsSe4)] (Ln = La(1a), Ce(1b), Nd(1c)), [Ln(en)4]AsSe4·0.5en (Ln = Sm(1d), Gd(1e), Dy(1f)), [Ln(dien)2(μ-η1,η2-AsSe4)] (Ln = La(2a), Ce(2b), Pr(2c)), [Ln(en)(trien)(μ-η1,η2-AsSe4)] (Ln = La(3a), Nd(3b)) and [Sm(en)(trien)(η2-AsSe4)] (3c) were prepared. Systematic investigations of the three systems clarify the relationship between the molecular structures of the synthetic lanthanide selenidoarsenates and the metal size evolution of the lanthanide series. Meanwhile, the coordination modes of the [AsSe4]3− tetrahedral anion to the same lanthanide ion are dependent on the denticity of ethylene polyamine as the second ligand. The lanthanide selenidoarsenates exhibit semiconducting properties with Eg between 2.15 and 2.31 eV.
Co-reporter:Ruihong Chen, Weiwei Tang, Jingjing Liang, Wenqing Jiang, Yong Zhang and Dingxian Jia
Dalton Transactions 2012 - vol. 41(Issue 40) pp:NaN12445-12445
Publication Date(Web):2012/08/16
DOI:10.1039/C2DT30960B
Solvothermal reactions of elements Ge and Se with Ln2O3 in a pentadentate polyamine, tetraethylenepentamine (tepa), produced novel neutral lanthanide–selenidogermanate polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n (Ln = Eu 1, Gd 2, Dy 3). The reaction with Dy2O3 in ethylenediamine (en) afforded an ionic selenidogermanate [{Dy(en)3}2(μ-OH)2]Ge2Se6 (4). In compounds 1–3, the Ln3+ ions are coordinated by a tepa and two OH− ligands to form binuclear [{Ln(tepa)}2(μ-OH)2]4+ fragments. Two GeSe4 tetrahedra are linked through two Se–Se bonds to form a novel [Ge2Se8]4− unit containing a six-membered Ge2Se4 ring in the chair conformation. The [Ge2Se8]4− unit acts as a bridging ligand via the trans terminal Se atoms to interlink the [{Ln(tepa)}2(μ-OH)2]4+ fragments into one-dimensional polymers [{Ln(tepa)(μ-OH)}2(μ-Ge2Se8)]n. Compounds 1–3 are the first examples of solvothermally prepared lanthanide complexes with a selenidogermanate anion as a ligand. The [Ge2Se6]4− anion in 4 is composed of two GeSe4 tetrahedra sharing a common edge, and is charge compensated by a [{Dy(en)5}2(μ-OH)2]4+ complex cation. The formation of the [Ge2Se8]4− and [Ge2Se6]4− anions and their behavior towards lanthanide ions in 1–4 show the significant influence of ethylene polyamines on the solvothermal synthesis of Ln selenidogermanates.
Co-reporter:Jingjing Liang, Jiangfang Chen, Jing Zhao, Yingli Pan, Yong Zhang and Dingxian Jia
Dalton Transactions 2011 - vol. 40(Issue 11) pp:NaN2637-2637
Publication Date(Web):2011/02/04
DOI:10.1039/C0DT01424A
Two systems, Ln/Sn/Se/en and Ln/Sn/Se/dien, were investigated under solvothermal conditions, and novel lanthanide selenidostannates [{Ce(en)4}2(μ-Se2)]Sn2Se6 (1a), [{Ln(en)3}2(μ-OH)2]Sn2Se6 (Ln = Pr(1b), Nd(1c), Gd(1d); en = ethylenediamine), [{Ln(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞ (Ln = Ce(2a), Nd(2b)), and [Hdien][Gd(dien)2(μ-SnSe4)] (2c) (dien = diethylenetriamine) were prepared and characterized. Two structural types of lanthanide selenidostannates were obtained across the lanthanide series in both systems. In the Ln/Sn/Se/en system, two types of binuclear lanthanide complex cations [Ce2(en)8(μ-Se2)]4+ and [{Ln(en)3}2(μ-OH)2]4+ (Ln = Pr, Nd, Gd) were formed depending on the Ln3+ ions. The complex cations are compensated by the [Sn2Se6]4− anions. In the Ln/Sn/Se/dien system, coordination polymer [{Ln(dien)2}4(μ4-Sn2Se9)(μ-Sn2Se6)]∞ and ionic complex [Hdien][Gd(dien)2(μ-SnSe4)] are obtained along the lanthanide series, among which the μ4-Sn2Se9, μ-Sn2Se6 and μ-SnSe4 ligands to the Ln3+ ions were observed. The formation of title complexes shows the effects of lanthanide metal size and amino ligand denticity on the lanthanide selenidostannates. Complexes 1a-2c exhibit semiconducting properties with band gaps between 2.08 and 2.48 eV.
Co-reporter:Wang Fang, Chunying Tang, Ruihong Chen, Dingxian Jia, Wenqing Jiang and Yong Zhang
Dalton Transactions 2013 - vol. 42(Issue 42) pp:NaN15158-15158
Publication Date(Web):2013/08/19
DOI:10.1039/C3DT51829A
Heterometallic Pb–Ag iodometallates [Ln(DMF)8]2Pb3Ag10I22 [Ln = Ce(1), Pr(2)] were prepared by the reactions of PbI2, AgNO3 and KI in dimethylformamide (DMF) templated by [Ln(DMF)8]3+ complexes formed in situ by stirring LnCl3 in DMF. The same reactions in the absence of AgNO3 or PbI2 afforded iodoplumbate [Pr(DMF)9]2[Pr(DMF)8]Pb11I31 (3), and iodoargentates [Ln(DMF)8]Ag6I9 [Ln = Ce(4), Pr(5)], respectively. Compounds 1 and 2 contain a ternary one-dimensional polymeric [Pb3Ag10I22]6− anion self-assembled from five AgI4, one PbI6 and one PbI4 primary units via edge- and face-sharing. Twelve PbI6 octahedra are interlinked via sharing of common faces to generate a 1D zigzag [Pb11I319−]n chain in 3, which represents a new member of iodoplumbate aggregates. In 4 and 5, three AgI4 tetrahedra connect through common edges to form the [Ag6I12]6− building block. The [Ag6I12]6− blocks are further interlinked by sharing common edges, resulting in the 1D [Ag6I93−]n chain. Optical absorption spectra showed that the synthesized Ag-iodoplumbate and iodoplumbate have potential for being used as semiconductors. Our results show that heterometallic halometallate properties can be tuned by combining structural units with different symmetries, enabling the synthesis of specific functional materials.
Co-reporter:Yali Shen, Jialin Lu, Chunying Tang, Wang Fang, Dingxian Jia and Yong Zhang
Dalton Transactions 2014 - vol. 43(Issue 24) pp:NaN9125-9125
Publication Date(Web):2014/04/07
DOI:10.1039/C4DT00358F
Hybrid organic–inorganic Pb–Ag heterometallic iodides [(en)2(PbAgI3)]2n·nH2O (1), [(pda)2(PbAgI3)]n (2), [(tmeda)(PbAgI3)]n (3), [(trien)(PbAgI3)]n (4), [(tepa)(PbAg2I4)]n (5), and [{(dien)3(CO3)}2(Pb6Ag8I15)]nIn (6) were prepared by the reactions of PbI2, AgI (or Ag2CO3) and KI with different polyamines in N,N′-dimethylformamide (DMF) solution. In 1–4, two AgI4 tetrahedra share a common edge to form the bimeric Ag2I6 unit. It coordinates to the Pb(II) ion of [PbL2]2+ or [PbL′]2+ (L = en, pda; L′ = tmeda, trien) via iodine atoms to form hybrid organic–inorganic heterometallic iodides 1, 2, 3 and 4, respectively. Compounds 1, 3, and 4 contain 2-D layered backbones of [PbAgI3]n, whereas 2 contains a backbone of [PbAgI3]n with a 3-D structure. Steric hindrance and denticity of the ethylene polyamines influence the coordination modes and connection strength between the iodoargentate aggregates and Pb(II) ions. In 5, the AgI4 units are joined via sharing common edges to form a 1-D polymeric [Ag2I4]n2n− anion. It is connected with [Pb(tepa)]2+via iodine atoms to form a 3-D network of [(tepa)(PbAg2I4)]n. In 6, the CO32− ion binds three [Pb(dien)]2+ units to form the novel trinuclear [{Pb(dien)}3(μ3-CO3)]4+ complex ion. Eight AgI4 tetrahedra are connected via sharing common edges to give a novel Ag8I15 cluster with C3 symmetry. The Ag8I15 cluster and the [{Pb(dien)}3(CO3)]4+ unit are connected to form a novel layered heterometallic iodometallate cation [{(dien)3(CO3)}2(Pb6Ag8I15)]nn+via sharing iodine atoms. Compounds 1–6 represent a new type of hybrid organic–inorganic heterometallic iodide containing coordinative organic components. Optical absorption spectra show a blue shift of the absorption edges for 1–6 compared with those of the bulk PbI2 and AgI solids.
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