•Four mononuclear ruthenium(II)/(III) carboxylato complexes were synthesized.•The new ruthenium carboxylato complexes were characterized by X-ray crystallography.•Molecular orbital calculations of complexes 1–3 were presented.Reaction of [Ru(PPh3)3Cl2] with the 2-methyl-acrylic acid 3-trimethoxysilane propyl ester in the presence of triethylamine (Et3N) afforded the neutral 17e ruthenium(III)-carboxylato complex [RuCl2{κ2-O,O-O2CCCH2(CH3)}(PPh3)2] (1) as a result of the break of ester functional group. Interaction of [Ru(PPh3)3Cl2] with 2-chlorobenzoic acid under similar reaction conditions gave the 17e carboxylato ruthenium(III) complex [RuCl2(κ2-O,O-O2CC6H4-2-Cl)(PPh3)2] (2). Treatment of 2 with two equivalent n-BuLi, followed by addition of SO2 and Et3N resulted the cyclometalated 18e ruthenium(II) complex [Et3NH][RuCl(SO2)(κ2-C,O-C6H4-2-CO2)(PPh3)2] (3). When [Et4N]Cl was used instead of SO2 and Et3N, the reaction yielded the cyclometalated 18e ruthenium(II) complex [Et4N]2[RuCl2(κ2-C,O-C6H4-2-CO2)(PPh3)2] (4). Formation mechanisms of complexes 3 and 4 are supposed. The four complexes were spectroscopically characterized and the crystal structures of complexes 1–3 have been established by X-ray crystallography. Molecular orbital calculations of complexes 1–3 are presented by the B3LYP functional methods.Four mononuclear ruthenium(III)-carboxylato complexes [RuCl2{κ2-O,O-O2CCCH2(CH3)}(PPh3)2] (1) and [RuCl2(κ2-O,O-O2CC6H4-2-Cl)(PPh3)2] (2), and cyclometalled ruthenium(II) carboxylato complexes [Et3NH][RuCl(SO2)(κ2-C,O-C6H4-2-CO2)(PPh3)2] (3) and [Et4N]2[RuCl2(κ2-C,O-C6H4-2-CO2)(PPh3)2] (4) were synthesized and structurally characterized, and molecular orbital calculations of complexes 1–3 were presented by the B3LYP functional methods.Download high-res image (64KB)Download full-size image

•Six ruthenium(II)/(III) complexes bearing ONS-Schiff-base ligands were synthesized.•ll the synthesized complexes were characterized by X-ray crystallography.•The ruthenium complex was tested as catalyst for oxidation of 1-phenylethanol.Reaction of [Ru(PPh3)3Cl2] with 2-(methylthio)phenylsalicylaldimine Schiff-base (HL) in tetrahydrofuran (THF) in the presence of triethylamine afforded a ruthenium(II) complex [Ru(ONS-L)(PPh3)2Cl]·CH3OH·2.75H2O (1). Similarly, reaction of [Ru(CO)2Cl2] with HL in N,N′-dimethylformamide (DMF) in the presence of triethylamine gave a ruthenium(II) complex [Ru(ONS-L)(CO)2Cl] (2), while the reaction between [Ru(CO)2Cl2] and HL without base resulted in a ruthenium(III) complex [Ru(ONS-L)(CO)Cl2] (3). Treatment of RuCl3·3H2O with HL in ethanol in the presence of triethylamine gave an anionic complex [Et3NH][Ru(ONS-L)Cl3] (4), which reacted with [Cp∗2Ru] in the presence of sodium hydroxide to give complex [Cp∗Ru(η6-1,2,3,4-Me4C6H2)][Ru(ONS-L)Cl3]·CH2Cl2 (5) with a different cation. Besides, reaction of 4 and AgNO3 afforded a dinuclear ruthenium(II) complex [Ru2(ONS-L)(μ-ONS-L)2Cl]·CH2Cl2 (6). The structures of complexes 1–6 have been established by X-ray crystallography, of which complex 4 was selected as a catalyst for the typical oxidation of 1-phenylethanol to the according acetophenone.Six ruthenium(II) and ruthenium(III) complexes bearing tridentate monoanionic Schiff base ligands were synthesized and characterized by spectroscopic methods and single-crystal X-ray diffraction.Download high-res image (77KB)Download full-size image

•A new facial tris-cyclometalated iridium(III) complex fac-Ir(dmpopopz)3 was synthesized.•The new iridium(III) complex was characterized by X-ray crystallography.•Molecular orbital calculations of the complex were presented.•This complex was found to be an intense red emitter.The facial tris-cyclometalated iridium(III) complex fac-Ir(dmpopopz)3 (dmpopopzH = 1-(2,6-dimethylphenyloxy)-4-(4-phenyloxyphenyl)-phthalazine) was synthesized from the reaction of iridium(III) chloride hydrate and ligand dmpopopzH in refluxing ethoxyethanol. The conformation of complex fac-Ir(dmpopopz)3 is described on the basis of the 1H NMR, 13C NMR, FT-IR and mass spectroscopies, the crystal structure of fac-Ir(dmpopopz)3 was determined by X-ray crystallography, and the theoretical calculation of complex fac-Ir(dmpopopz)3 was also investigated by the DFT method. The absorption and emission spectral results exhibit that complex fac-[Ir(dmpopopz)3] may be used as a red-emitting phosphorescent material. Efficient OLEDs have been achieved using the complex fac-[Ir(dmpopopz)3] in the red-emitting region.A new facial tris-cyclometalated iridium(III) complex fac-Ir(dmpopopz)3 bearing aryl substituted phthalazine ligands has been synthesized and structurally characterized. This complex was found to be an intense red emitter and charge neutral which may be desirable for an example in the OLED applications.Download high-res image (58KB)Download full-size image

Ultrathin graphitic carbon nitride nanosheets with huge specific surface areas and exceptional photocatalytic performance of hydrogen evolution are prepared via a facile secondary calcination approach.

Reactions of substituted 2-(chloromethyl)-pyridine (1a–1b) and substituted imidazole-2-thione (2a–2c) in the presence of sodium methoxide afforded a series of substituted [4-(2,2,2-trifluoroethoxy)-2-pyridinyl]-methylthio-imidazoles (3a–3f) in good yields. Similar reactions of compounds 1a–1b with different pyrimidine-2-thiol (4a–4b) led to the corresponding [4-(2,2,2-trifluoroethoxy)-2-pyridinyl]-methylthio-pyrimidine (5a–5d, av. 90 %) derivatives. Molecular structures of compounds 3a and 5b were confirmed by single-crystal X-ray diffraction analyses. The unit cells of both compounds have monoclinic P21/c symmetry with the cell parameters a = 7.786(7), b = 21.910(19), c = 8.675(8) Å, β = 91.113(13)°, and V = 1480(2) Å3 for 3a and a = 9.1683(13), b = 14.0946(19), c = 12.5409(18) Å, β = 93.686(2)°, and V = 1617.2(4) Å3 for 5b.

Treatment of a series of substituted resorcin[4]arenes in pyridine with dichlorophenyl-phosphine followed by addition of selenium powder resulted in the formation of the corresponding selenophosphatocavitands [R2CHC6HR1O2PSePh]4 (R1 = H, R2 = CH2CH2Ph, 1; R1 = CH3, R2 = CH3, 2; R1 = CH3, R2 = C2H5, 3) in moderate yields. All compounds were spectroscopically characterized, of which the structure of 3·CHCl3 has been established by X-ray crystallography. The molecular structure of 3 shows that the selenophosphato-cavitand adopts C4v bowl-shaped conformation with four P=Se bonds oriented toward the molecular cavity.

Treatment of [Et4N]2[WSe4] with AgX (X = Br, I) in a 1:3 ratio in DMF or DMF/CH3CN afforded tetranuclear cubane-like heteroselenometallic clusters [Et4N]3[(μ3-X)(μ3-WQSe3)(AgX)3] (X = Br, Q = Se 1; X = Br, Q = O 2; X = I, Q = Se 3). While the reaction of [Et4N]2[WSe4] with two equivalents of AgBr in DMF gave a hexanuclear cage heteroselenometallic cluster [Et4N]4[(μ3-WO0.83Se3.17)2(AgBr)4] (4). Treatment of [Et4N]2[WSe4] with three equivalents of AgCl in DMF in the presence of the bidentate phosphine ligand bis-(diphenylphosphino)-ethane (dppe) or bis-(diphenylphosphino)-propane (dppp) resulted in the isolation of octanuclear heteroselenometallic clusters [Et4N]4[{(μ3-Cl)(μ3-WSe4)Ag3Cl2}2(μ-dppe)] (5) and [Et4N]2[{(μ3-WSe4)Ag3Cl2}2(μ-dppp)2] (6) with double-cubane. All clusters are anionic and air-stable in the solid-state, and were characterized by electronic, infrared, mass and NMR spectroscopies, and their molecular structures have been also established by X-ray crystallography. The nonlinear optical properties of clusters 1–6 were examined by z-scan techniques with 7 ns pulses at 532 nm, and the optical limiting effects of clusters 1–6 were also determined for the comparison with the related argentoselenometallic clusters in this paper.A series of tetra-, hexa- and octa-nuclear anionic argento-selenotungstates have been synthesized and characterized by spectroscopy and X-ray crystallography. The nonlinear optical properties and optical limiting effects of these silver-containing heteroselenometallic clusters were also determined for the investigation of the structure–property relationship.

Co-crystallization of C-ethyl-calix[4]resorcinarene (1) and 4,4′-bipyridine (4,4′-bipy) from ethanol in the presence of ferrocene (FcH) yielded a multi-component complex FcH@1·2(4,4′-bipy) (3) that consists of a one-dimensional wave-like polymer, 1·2(4,4′-bipy), in which the cavity of 1 is deepened supramolecularly to enclose ferrocene as a guest. Heating mixture of C-methyl-calix[4]resorcinarene (2), trans-1,4-bis-(pyridyl)ethylene (bpe) and FcH in ethanol led to isolation of a similar host–guest complex FcH@2·2(bpe)·0.5C6H14 (4) in which the FcH guests have been assembled within a wave-like framework (2)·2(bpe).

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4′-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4′-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

•Ruthenium(II) complexes with pyridine-2,6-dicarboxylato ligands were synthesized.•The synthesized complexes were characterized by single-crystal X-ray diffraction.•Easy substitution reactions occurred by N-donors on coordinated water molecule.Reaction of [Ru(COD)Cl2]x (COD = 1,5-cyclooctadiene) with pyridine-2,6-dicarboxylic acid (dipicH2) in the presence of Et3N afforded an anionic complex [Et3NH][(dipic)(COD)RuCl] (1) with a κ3-dipic coordination mode. Treatment of 1 with AgNO3 in MeOH/H2O afforded a neutral complex [(dipic)(COD)Ru(H2O)] (2) in a high yield. Reaction of 2 with 1 equiv. of L gave the according adducts [(dipic)(COD)Ru(L)] (L = py (py = pyridine, 3), 4-t-Bupy (4), NH3 (5), t-BuNH2 (6), PhCH2NH2 (7), and MeCN (8)), while the similar reaction with 0.5 equiv. of 4,4′-bipyridine afforded a binuclear complex [{(dipic)(COD)Ru}2(μ-bipy)] (bipy = 4,4′-bipyridine, 9). All complexes have been spectroscopically characterized along with the electrochemical analyses, and the structures of complexes 1–4, 7·MeOH and 9·2H2O have been also determined by single-crystal X-ray diffraction.Treatment of AgNO3 with the anionic complex [Et3NH][(dipic)(COD)RuCl] afforded a neutral aqua complex [(dipic)(COD)Ru(H2O)], which reacted easily with various N-donor ligands to yield the corresponding mono- and bi-nuclear ruthenium complexes by way of the typical substitution reactions.

•Seven mono- and binuclear ruthenium complexes were synthesized.•The synthesized complexes were characterized by different spectroscopic techniques and X-ray crystallography.•Different coordination modes of pyridine-2,6-dicarboxylate were observed.Treatment of RuCl3·3H2O, [Et4N][RuCl4(CH3CN)2] or [Ru(DMSO)4Cl2] with the ligand pyridine-2,6-dicarboxylic acid (dipicH2) in the presence of Et3N afforded the mononuclear complex [Et3NH]2[Ru(κ3-dipic)Cl3] (1), [Et4N][Ru(κ3-dipic)(MeCN)Cl2] (2) or [Et3NH][Ru(κ3-dipic)-(DMSO)2Cl] (4), respectively, with a κ3-dipic coordination mode. Reaction of [Ru(CO)2Cl2]x or [Ru(NO)(PPh3)2Cl3] with dipicH2 in the presence of Et3N gave the mononuclear complex [Et3NH]2[Ru(κ2-dipic)(CO)2Cl2] (3) or [Et3NH][Ru(κ2-dipic)(NO)(PPh3)Cl2] (5), respectively, with a κ2-dipic coordination mode. Reaction of [Et4N][RuCl4(CH3CN)2] with dipicH2 in the presence of AgNO3 in EtOH/MeCN resulted in a dianionic Ru(III) complex, [Et4N]3[Ru(κ3-dipic)2][Ru(κ3-dipic)(κ2-dipic)Cl] (6), with the mixed κ3-dipic and κ2-dipic coordination modes. Interaction of RuCl3·3H2O with dipicH2 and Et3N gave the dinuclear Ru(III) complex [Et3NH]2[Ru(κ3-dipic)(μ2-κ1,κ2-dipic)]2 (7) with a bridging μ-κ1,κ2-dipic coordination mode. All complexes have been spectroscopically characterized along with the electrochemical analyses. The structures of 1, 2, 3·H2O, 4, 5·½Et2O, 6·CH2Cl2·C6H14, 7·CH2Cl2 have been also determined by single-crystal X-ray diffraction.Treatment of the ruthenium starting complexes with pyridine-2,6-dicarboxylic acid (dipicH2) in the presence of Et3N gave a series of Ru(II)/Ru(III) complexes with a κ3-dipic, κ2-dipic and/or μ2-κ1,κ2-dipic coordination mode ligands. A new dinuclear ruthenium(III) complex [Et3NH]2[Ru(κ3-dipic)(μ2-κ1,κ2-dipic)]2 features a bridging μ2-κ1,κ2-dipic coordination mode is found for the dipic2− ligand.

Ternary supertetrahedral chalcogenolate clusters were interlinked with bipyridines into a microporous semiconducting framework with properties qualitatively different from those of the original clusters. Both the framework and the clusters were effective photocatalysts, and rapidly degraded the dye rhodamine B.

•Rhenium–sulfur–copper cubane-like cluster compounds.•Syntheses and structures of the compounds with the bridging sulfate anions.•The first examples for the Re/Cu clusters with the bridging sulfate anions.Treatment of [Et4N][ReS4] with three equivalents of CuSO4·5H2O in the presence of three equivalents PPh3 gave a tetranuclear cubane-like cluster compound [(μ3-SO4)(μ3-ReS4)Cu3(PPh3)3]·2dmf (1·2dmf) in which a ReS4Cu3 core is capped by a μ3-SO42− moiety, leaving a SO double bond. A similar reaction of [Et4N][ReS4] with three equivalents of CuSO4·5H2O in the presence of two equivalents of PPh3 gave rise to isolation of a neutral one-dimensional polymeric cubane-like cluster compound [(μ4-SO4)(μ3-ReOS3)Cu3(PPh3)2]n (2) in which the ReOS3Cu3 cores are bridged by the μ4-SO42− anions. Both cluster compounds were characterized by single-crystal X-ray diffraction along with the spectroscopic methods.A tetranuclear cubane-like cluster compound [(μ3-SO4)(μ3-ReS4)Cu3(PPh3)3]·2dmf contains a ReS4Cu3 core capped a μ3-SO42− moiety and a neutral one-dimensional polymeric cubane-like cluster compound [(μ4-SO4)(μ3-ReOS3)Cu3(PPh3)2]n contains the ReOS3Cu3 cores bridged by the μ4-SO42− anions.

•Four rhodium complexes with dithioimidodiphosphinate ligand were prepared.•The synthesized complexes were characterized by X-ray crystallography.•C–H activation of [N(R2PS)2]− (R = alkyl) with Rh2(OAc)4 was observed.•Break of Rh–Rh bond and oxidation of Rh(II) to Rh(III) species was observed.Treatment of dirhodium(II) tetra-acetate Rh2(OAc)4 with HN(Ph2PS)2 in refluxing tetrahydrofuran (THF) yielded a typical mononuclear Rh(III) complex Rh[N(Ph2PS)2]3 (1). Reaction of Rh2(OAc)4 with HN(iPr2PS)2 in a similar condition resulted in the mixed Rh(III) complexes Rh[N(iPr2PS)2)]3 (2) in a major product and Rh[N(iPr2PS)2][κ2S,κC-N(iPr2PS)(iPr(C3H6)PS)] (3) in a minor product, while the similar reaction by use of HN(tBu2PS)2 led to isolation of complex Rh[N(tBu2PS)2][κ2S,κC-N(tBu2PS)(tBu(C4H8)PS)] (4) as a sole product. Novel C–H bond activation of one methyl group in the ligands [N(R2PS)2]− (R = iPr, tBu) was observed in complexes 3 and 4, which was further confirmed by the analysis of X-ray crystallography along with other spectroscopic properties.Two σ-alkyl rhodium(III) complexes Rh[N(iPr2PS)2][κ2S,κC-N(iPr2PS)(iPr(C3H6)PS)] and Rh[N(tBu2PS)2][κ2S,κC-N(tBu2PS)(tBu(C4H8)PS)] containing ortho-metalated bis(dialkylthiophosphoryl)imide ligand were isolated via C–H activation of [N(R2PS)2]− (R = iPr, tBu) and oxidation of dirhodium(II) tetraacetate Rh2(OAc)4.

•One-dimensional butterfly and cubane-like Ag-Se-W clusters bridged by dppe ligand•Crystal structures and nonlinear optical properties of Ag-Se-W cluster•An obviously efficient improvement in optical limiting effect is observed.Interaction of [Et4N]2[WSe4], AgBr and bis(diphenylphosphino)ethane (dppe) in a 1:2:1 ratio afforded the polymeric trinuclear cluster {[Et4N][(μ-Br)(μ3-WSe4)Ag2(μ-dppe)]}n (1), while the similar reaction of [Et4N]2[WSe4], AgCl and dppe in a 1:3:1 ratio in the presence of [Et4N]Br gave the polymeric tetranuclear cluster {[Et4N][(μ3-Br)(μ3-WSe4)Ag3Cl(μ-dppe)]}n (2). Two one-dimensional butterfly and cubane-like argento-selenotungstate clusters bridged by dppe ligands were characterized by single crystal X-ray diffraction and the optical limiting properties of polymeric cluster 2 with non-central symmetry were also investigated.The synthetic protocols for one-dimensional polymeric heteroseleno-metallic clusters as demonstration {[Et4N][(μ-Br)(μ3-WSe4)Ag2(μ-dppe)]}n (1) with the butterfly type and {[Et4N][(μ3-Br)(μ3-WSe4)Ag3Cl(μ-dppe)]}n (2) with the cubane-like type are firstly reported, which are constructed by linking up monomeric inorganic cluster with organic bridging ligands.

Hydrothermal treatment of halide mono-substituted complex of (Me4N)2[Cd4(SPh)9Cl] (1) afforded three-dimensional framework [Cd4(SPh)8]n (2), its three-dimensional framework can be destroyed by coordination with PPh3 ligand, forming a polymeric complex of [Cd4(SPh)8(PPh3)]n (3) with one-dimensional zig–zig chain structure. Complexes 1, 2 and 3 were structurally characterized by single crystal X-ray structure analysis. Their diffuse reflectance spectra and photoluminescence properties were also investigated at room temperature.

Highlights•Two thiolato-bridged poly-nuclear ruthenium carbonyl complexes were synthesized.•The synthesized complexes were characterized by X-ray crystallography.•The clusters display unique eight and twelve metallomacrocycle rings, respectively.Two aryl-thiolato-bridged ruthenium carbonyl chloro clusters were synthesized from reactions of [Ru(CO)2(μ-Cl)2]n and sodium arylthiols. The tetra- and hexa-nuclear clusters display unique eight and twelve metallomacrocycle rings with Ru4S4 and Ru6S6 cores, respectively.Graphical abstractThe tetra- and hexa-nuclear ruthenium carbonyl clusters display unique eight and twelve metallomacrocycle rings with Ru4S4 and Ru6S6 cores, respectively.

•Mono- and bi-nuclear Ru(II)/Ru(III) complexes with 1-aryl-2-mercaptoimidazole ligand were synthesized.•Mononuclear Ru(II) complexes with tris(2-mercapto-1-arylimidazolyl)borate ligand were prepared.•X-ray crystallography were performed on the synthesized complexes.Treatment of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with 1-(4-chlorophenyl)imidazole-2-thione (HtimAr) in tetrahydrofuran (THF) at reflux afforded the mononuclear complex [Ru(κ1-S-HtimAr)2(PPh3)2Cl2] (1) and [RuH(CO)(κ1-S-HtimAr)(PPh3)2Cl] (4), respectively, whereas interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with HtimAr in the presence of NaOMe in THF gave the mononuclear complex cis-[Ru(κ2-S,N-timAr)2(PPh3)2] (2) and [RuH(CO)(κ2-S,N-timAr)(PPh3)2] (5), respectively. Reaction of [RuCl2(PPh3)3] with 1 equiv. of HtimAr in the presence of Et3N and H2O2 gave a Ru(III) complex, [Ru(κ2-S,N-timAr)(PPh3)2Cl2] (3). Reaction of [(η6-p-cymene)RuCl(μ-Cl)]2 with HtimAr in THF at reflux in the presence of NaOMe and K[PF6] gave the μ-S,N-timAr-bridged dinuclear complex [{(η6-p-cymene)Ru}2{μ-η1(S), η1(N)-timAr}{μ-η2(S), η1(N)-timAr}{κ1-S-HtimAr}][PF6]2 (6). Reaction of [RuHCl(CO)(PPh3)3] or [Ru(PPh3)3Cl2] with the bulky ligand [HB(timAr)3]− at reflux resulted a ruthenaboratrane complex, [Ru(CO){κ4-B,S,S,S-B(timAr)3}(PPh3)] (7) and a typical Ru⋯H–B complex, [Ru{κ3-H,S,S-HB(timAr)3}(κ2-S,N-timAr)(PPh3)] (8), respectively. All complexes have been spectroscopically and electrochemically characterized. The structures of 1·CH2Cl2, 2, 3·CH2Cl2, 4·C6H14, 6, 7·CH3OH·0.5H2O, and 8·0.5C6H14·0.5CH2Cl2·2H2O have also been determined by single-crystal X-ray diffraction.Treatment of the ruthenium staring complexes with 1-(4-chloro-phenyl)imidazole-2-thione (HtimBz) in tetrahydrofuran gave a series of ruthenium complexes with HtimBz and/or [timBz]− ligands. A new ruthenaboratrane complex [Ru(CO){κ4-B,S,S,S-B(timBz)3}(PPh3)] features a ruthenium-boron dative bond and a typical Ru⋯H–B complex [Ru{κ3-H,S,S,-HB(timBz)3}(κ2-S,N-timBz)(PPh3)] shows a strong agostic Ru⋯H–B interaction.

Calcium vanadate nanorods with sheaf-shaped structures have been synthesized by a facile hydrothermal route using calcium acetate and sodium orthovanadate as the raw materials. The as-prepared calcium vanadate nanorods are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and infrared and photoluminescence (PL) spectroscopy. Calcium vanadate nanorods exhibit single crystalline structure and XRD confirms the crystal structure to be hexagonal Ca10V6O25 phase. The average diameter and length of the calcium vanadate nanorods are about 50 nm and 3 μm, respectively. A possible formation process of the nanorods has been elucidated.

Treatment of [Ru(PPh3)3Cl2] with two equiv. of K[H2B(timMe)2] (timMe = N-methyl-2-mercaptoimidazol-1-yl) in tetrahydrofran (THF) at room temperature afforded a neutral complex [Ru(PPh3){κ3-H,S,S′-H2B(timMe)2}{κ2-S,S′-H2B(timMe)2}] (1), while reaction of the similar reactants in THF at reflux gave a cationic complex [Ru(PPh3){κ3-H,S,S′-H2B(timMe)2}(η1-S-HtimMe)2}]Cl (2) during which the fragmentation of the ligand [H2B(timMe)2]− occurred due to higher temperature. Treatment of [Ru(DMSO)4Cl2] with two equiv. of K[H2B(timMe)2] in THF solution at room temperature resulted in formation of a neutral complex [Ru{κ3-H,S,S′-H2B(timMe)2}2] (3) with a [RuS4H2] core. The crystal structures of complexes 1–3 have been determined by single-crystal X-ray diffraction, establishing the configuration and the B–H⋯Ru bonding mode of the ligands. The ruthenium atom in each of the above complexes adopts a pseudo-octahedral geometry with a three-center, two-electron B–H⋯Ru interaction. Spectroscopic and electrochemical properties of all complexes are also reported.Graphical abstractThree ruthenium complexes with dihydridobis(N-methyl-2-mercaptoimidazolyl)-borate ligands ([H2B(timMe)2]−) containing borohydrido and mercapto groups have been synthesized. X-ray diffraction studies of these complexes established the configuration and the B–H⋯Ru bonding mode of the ligands, which are achieved through the coordination of two sulfur atoms and one B–H bond to the central ruthenium atom.Highlights► Ruthenium–sulfur complexes for homogeneous catalysis. ► Ruthenium complexes with [H2B(timMe)2]− ligands. ► The configuration and the B–H⋯Ru bonding mode of [H2B(timMe)2]−. ► Spectroscopic and electrochemical properties of ruthenium complexes.

Reaction of [Me4N]2[Cd(SPh)4] and [Ag(PPh3)2NO3] (molar ratio = 1:1) in MeOH/CH2Cl2 (1:1) followed by recrystallization from DMF/Et2O yielded a neutral heptanuclear cluster, [Cd3(μ-SPh)6(μ3-SPh)4Ag4(PPh3)4] (1), while interaction of [Me4N]2[Cd(SPh)4] with AgNO3 and dppp (molar ratio = 4:6:3) gave a neutral undecanuclear cluster [Cd3(OMe)2(μ-SPh)4(μ3-SPh)8Ag8(μ-dppp)4] (2). Crystal structures and photoluminescent properties of the two clusters in solid state were reported.Two neutral heterometallic cadmium(II)/silver(I) clusters of phenylthiolates, a heptanuclear [Cd3(μ-SPh)6(μ3-SPh)4Ag4(PPh3)4] and a undecanuclear [Cd3(OMe)2(μ-SPh)4(μ3-SPh)8Ag8(μ-dppp)4] with phosphine ligands, were synthesized and structurally characterized.Highlights► Polynuclear Cd(II)/Ag(I) heterobimetallic clusters of phenylthiolates. ► Reaction of the homolepic [Cd(SPh)4]2– anion with silver(I) ion. ► The design and syntheses of polynuclear heterometallic clusters based on [Cd(SPh)4]2– as a metalloligand in the photoluminescenct application.

Interaction of CuCl with a mixture of NaTePh and anhydrous CdCl2 in tetrahydrofuran (THF) in the presence of PPh3 ligand led to the isolation of the ternary cadmium–copper–tellurolate cluster [CdCu4(μ-TePh)3(μ3-TePh)3(PPh3)4] (1) and the dodecanuclear mixed copper/telluride/tellurolate cluster [Cu12(μ6-Te)3(μ3-TePh)6(PPh3)6] (2), while the similar reaction with AgCl gave the ternary cadmium–silver–tellurolate cluster [CdAg4(μ-TePh)3(μ3-TePh)3(PPh3)4] (3) and the tetradecanuclear mixed silver/telluride/tellurolate cluster [Ag14(μ6-Te)(μ3-TePh)12(PPh3)8] (4). The binary clusters 2 and 4 were previously reported by Fenske and Corrigan, whereas clusters 1 and 3 are the first examples of ternary tellurolate-bimetallic clusters. Crystal structures and photoluminescent properties of the new ternary clusters 1 and 3 are reported in this paper.Preparation and structures of the ternary cadmium–copper(silver)–tellurolate clusters [CdM4(μ-TePh)3(μ3-TePh)3(PPh3)4] (M = Cu, Ag) are firstly reported and their photoluminescent properties in the solid state are also investigated.Highlights► New soluble ternary cadmium–copper(silver)–tellurolate clusters. ► The first examples of ternary telluralate-bimetallic clusters. ► Crystal structures and photoluminescent properties of the new ternary clusters.

A new cyclometalated iridium(III) complex, Ir(ppz)2(dtp) (Ir1) (ppzH = 4-phenylphthalazinone, dtp = diethyl dithiophosphate), has been synthesized and characterized by single-crystal X-ray diffraction. The photoluminescence spectrum of Ir1 shows an emission maximum at 597 nm and its quantum yield is ca. 0.072. Complex Ir1 exhibits a strong and fast decrease of emission upon addition of Ag+ in aqueous media. The ratio of Ir1 responding to Ag+ was determined to be 1:1 by UV–Vis absorption and phosphorescent emission measurements. Complex Ir1 is a highly selective chemosensor for Ag+ over other transition metal ions.

Treatment of [Hg(EPh)2] with 2 equivalents of [Cu(PPh3)2Cl] gave the trinuclear Hg/Cu/S(Se) complexes [Hg(μ-EPh)2{CuCl(PPh3)2}] (E = S 1, Se 2) in which the two copper centers are ligated by the [PhE]− ligands of the [Hg(EPh)2]. A similar reaction of [Hg(EPh)2] with [Ag(PPh3)2Cl] gave rise to isolation of the dinuclear compounds [Hg(SePh)(μ-SePh)(μ-Cl)Ag(PPh3)2] (E = S 3, Se 4) in which the coordination geometry of the mercury atom is a slightly distorted T-shape. Reactions of the homoleptic tetrahedral species [Cd(EPh)4]2− with 2 equivalents of [Cu(PPh3)2NO3] afforded the neutral linear trinuclear complexes [Cd(μ-EPh)4{Cu(PPh3)2}2] (E = S 5, Se 6) in which two [Cu(PPh3)2]+ fragments bind with the opposite edges of a tetrahedral [Cd(EPh)4]2− moiety via the sulfur or selenium atoms of the PhE− ligands. A similar reaction of [Me4N]2[Cd(SPh)4] with 2 equivalents of [Ag(PPh3)2NO3] gave an analogous complex [Cd(μ-SPh)4{Ag(PPh3)2}2] (7), whereas the reaction of [Me4N]2[Cd(EPh)4] with an equivalent amount of [Ag(PPh3)2NO3] under similar conditions afforded the neutral heptanuclear complexes [Cd3(μ-EPh)6(μ3-EPh)4(AgPPh3)4] (E = S 8, Se 9) which comprise three [(AgPPh3)]+ fragments side-ligated and one [(AgPPh3)]+ fragment side-capped with the trinuclear cadmium-thio(seleno)phenolate [Cd3(μ-EPh)9(μ3-EPh)]4− moieties via the sulfur atoms of thiophenolates in 8 and the selenium atoms of selenophenolates in 9. The nonlinear optical properties of two neutral heptanuclear complexes 8 and 9 have been examined by z-scan techniques with 7-ns pulses at 532 nm.Through the interactions of homoleptic [Hg(EPh)2] molecules and [Cd(EPh)4]2− anions (E = S, Se) as metalloligands with [M(PPh3)2Cl] or [M(PPh3)2NO3] (M = Cu, Ag), series of new heterobimetallic Cd(Hg)/Cu(Ag)/S(Se) complexes including neutral trinuclear [Hg(μ-EPh)2{CuCl(PPh3)2}2] and [Cd(μ-EPh)4{M(PPh3)2}2] and heptanuclear [Cd3(μ-EPh)6(μ3-EPh)4(AgPPh3)4] have been isolated and characterized. Their molecular structures and spectroscopic properties of these heterobimetallic complexes have been presented in this paper.

Metathesis reaction between equimolar amount of [Et4N][GaCl4] and Na2edt in methanol resulted in the formation of the dichloro complex [Et4N][Ga(edt)Cl2] (1), whereas reaction of [Et4N][GaCl4] with two equivalents of Na2edt in methanol gave the complex [Et4N][Ga(edt)2] (2) which can act as a metalloligand. Treatment of 2 with M(PPh3)2NO3 in DMF/CH2Cl2 afforded the heterobimetallic complexes [Ga(edt)2M-(PPh3)2] (M = Cu 3, Ag 4) in moderate yields. The structures of 1–4 were determined by single-crystal X-ray diffraction analyses. Both [Ga(edt)Cl2]− and [Ga(edt)2]− anions have a distorted tetrahedral geometry. The former consists of one five-membered ring formed by chelating dithiolate and two terminal chloride atoms while the latter consists of two five-membered rings formed by two the chelating dithiolates. Complexes 3 and 4 consist of metalloligand [Ga(edt)2]− anion chelated to [M(PPh3)2]+via the sulfur atoms. Both tetrahedrally coordinated Ga and Cu(Ag) atoms are bridged by two sulfur atoms, forming a planar “GaS2M” (M = Cu, Ag) core. Thermogravimetry analysis revealed that heterobimetallic complexes 3 and 4 decomposed to give the corresponding ternary metal sulfide materials.Heterobimetallic complexes [Ga(edt)2M(PPh3)2] (M = Cu, Ag) formed from the reactions of the metalloligand [Ga(edt)2]− with [M(PPh3)2]+ species. The potential application of such complexes as single-source precursors for ternary sulfide materials was investigated by thermogravimetry analysis.

Treatment of [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar = p-C6H4OMe) in the presence of ammonium hydroxide afforded the dinuclear complex [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(O)S2}]2 (1) in which the tripodal [ArP(O)S2]2− ligands bind to the ruthenium atom in both bridging and chelating modes with two non-coordinating PO groups. Interaction of [RuHCl(CO)(PPh3)3] with [ArP(S)(μ-S)]2 and bis(diphenylphosphino)methane (dppm) in the presence of ammonium hydroxide gave the dinuclear complex [Ru(CO){μ3-η1(O),η2(S,S′)-ArP(O)S2}(dppm)]2 (2) in which the tripodal [ArPOS2]2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Treatment of [Ru(PPh3)3Cl2] with [ArP(S)(μ-S)]2 at reflux in the presence of ammonium hydroxide led to the formation of the dinuclear mixed valence complex [Ru2Cl2(μ-S){μ3-η1(O),η1(S),-η2(S,S′)-ArP(O)S2}(PPh3)3] (3), which contains a [RuII(PPh3)2Cl]+ and [RuIV(PPh3)Cl]3+ moieties by the tripodal [ArPOS2]2− ligand in a μ3-η1(O),η1(S),η2(S,S′) coordination mode and the μ-S2− anion. The crystal structures of 1, 2, and 3·CH2Cl2 along with their spectroscopic and electrochemical properties are reported.Graphical abstractThe tripodal [ArP(O)S2]2− ligands in three dinuclear ruthenium–dithiophosphonate complexes [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(O)S2}]2 (1), [Ru(CO){μ3-η1(O),η2(S,S′)-ArP(O)S2}(dppm)]2 (2), and [Ru2Cl2(μ-S){μ3-η1(O),η1(S),-η2(S,S′)-ArP(O)S2}(PPh3)3] (3) show three different coordination modes μ-η1(S),η2(S,S′), μ3-η1(O),η2(S,S′), and μ3-η1(O),η1(S),η2(S,S′), respectively.Highlights► Dinuclear ruthenium complexes. ► Ruthenium dithiophosphonate complexes. ► The tripodal [ArP(O)S2]2− ligands showing three different coordination modes. ► The typical phosphor-1,1′-dithio ligand set.

A new neutral dimeric cyclometalated iridium complex containing bridging thiocyanate ligands, [{Ir(μ-SCN)(pqcm)2}2] (1, pqcmH = 2-phenyl-quinoline-4- carboxylic acid methyl ester), has been synthesized and structurally characterized. The photoluminescence (PL) spectrum of 1 shows emission maximum at 638 nm with a lifetime of 0.11 μs and the PL quantum yield is ca. 0.012. The phosphorescence behaviours of 1 towards different solvents and metal ions were also investigated and the strong phosphorescence quenching by acetonitrile and two equivalents of Hg2+, Cu2+ and Ag+ ions were observed.A neutral dimeric cyclometalated iridium complex containing bridging thiocyanate ligands has been synthesized and structurally characterized, and show a short lifetime of 0.11 μs and the quenching of phosphorescence in the presence of acetonitrile or two equivalents of Hg2+, Cu2+ and Ag+ ions.Highlights► Luminescent cyclometalated iridium(III) complexes. ► Cyclometalated iridium(III) thiocyanate-bridging dimer. ► Short lifetime and the quenching of phosphorescence. ► Phosphorescence behaviours towards metal ions.

Three new cadmium coordination polymers, [CdBr2(tmdp)2(μ-tmdp)2]n·n(H2O) (1), [Cd(SCN)2(μ-tmdp)2]n·2n(PhS) (2) and [Cd(SCN)2(μ-tmdp)2]n·n(Ph2S2)·n(CH3CN) (3) (tmdp = 4,4′-trimethylenedipyridine), have been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis. The geometry around cadmium is a slightly distorted octahedron with four tmdp and two Br- or SCN- ligands. Complex 1 represents a one-dimensional structure, whereas complexes 2 and 3 are two-dimensional coordination polymers. The rhombic channels of the coordination network of 2 and 3 are occupied by 1D polymeric (PhS)n and diphenyl disulfide (Ph2S2) molecules, respectively. The photoluminescent properties of coordination polymers 1–3 were investigated in solid state at room temperature. The TGA experiments showed that these three complexes were quite thermally stable.Three new cadmium coordination polymers have been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction analysis. The rhombic channels of the two-dimensional coordination networks are occupied by one-dimensional polymeric (PhS)n and diphenyl disulfide (Ph2S2) molecules.

The branch-shaped NaGdF4:Eu3+ nanocrystals (NCs) were synthesized by using polyvinylpyrrolidone (PVP) as a capping agent in ethylene glycol (EG) solution. The NCs were readily dispersed into water or ethanol to form a relatively stable suspension, which may facilitate their applications in biological fields. Meanwhile, the crystal structures of the NCs were tunable from the mixture of the α-(cubic) and β-(hexagonal) phases to the pure β-phase by varying the F−/Ln3+ molar ratio or the reaction temperature. The pure β-phase NCs were obtained at relatively high F−/Ln3+ molar ratio and reaction temperature. In addition, the Eu3+-doping concentration—dependent optical properties of the NaGdF4:Eu3+ NCs were investigated in detail. The result shows that the emissions from high energy level transitions (e.g., 5D1, 5D2, and 5D3) are significantly impaired with increasing the Eu3+-doping concentration due to the cross-relaxation process, and the emission at 612 nm is predominant since the doped Eu3+ ions locate in the crystal fields without inversion center.

Treatment of the dimeric [FcP(S)(μ-S)]2 [Fc = Fe(η5-C5H4)(η5-C5H5)] with the organic base Et3N in methylene chloride solution resulted in the isolation of a multi-component compound [Et3NH]2[(FcPO2S)2CH2][FcPS(OH)2]2·CH2Cl2 (1·CH2Cl2). The formation of the [(FcPO2S)2CH2]2− anion was due to the dechlorination of methylene chloride, it consists of two [FcPO2S]2− units bridging by a methylene group. Reaction of Na[FcP(OCH3)S2] with equal equivalent of [Cu(MeCN)4][ClO4] in methanol afforded a sole tetranuclear copper(I) complex Cu4[FcP(OCH3)(μ-S)(μ3-S)]4 (2). The neutral complex 2 consists of a crystallographically centrosymmetric tetramer containing four CuS3 arrays each of which has one μ-sulfur and two μ3-sulfur bridges.

Interaction of the dimer [(η6-p-cymene)RuCl(μ-Cl)]2 or [Cp∗RuCl(μ-Cl)]2 with two equiv. of K[HB(timMe)3] at reflux gave anionic complex [(η6-p-cymene)Ru{κ3-S,S,S-HB(timMe)3}]Cl (1) or neutral complex [Cp∗Ru{κ3-S,S,S-HB(timMe)3}] (2), respectively, with terminally non-coordinated BH bond. Complexes 1 and 2 were further refluxed in CHCl3 to result in the quantitative formation of [(η6-p-cymene)Ru{κ3-S,S,S-ClB(timMe)3}]Cl (3) and [Cp∗Ru{κ3-S,S,S-ClB(timMe)3}] (4), respectively, with BCl bonds. Treatment of [RuHCl(CO)(PPh3)3] or [Ru(PPh3)3Cl2] with equal equiv. of K[HB(timMe)3] at reflux afforded the neutral complex [RuH(CO)(PPh3){κ3-S,S,H-HB(timMe)3}] (5) or [Ru(PPh3)2Cl{κ3-S,S,H-HB(timMe)3}] (6), respectively, with an agostic BH⋯Ru bond. Complex 6 was further treated with one equiv. of NatimMe in THF solution to result in formation of new complex [Ru(PPh3)(κ2-S,N-timMe){κ3-S,S,H-HB(timMe)3}] (7) with chelating [timMe]– moiety. All complexes were spectroscopically characterized, of which the structures of 1·1/4C6H14, 4·C6H14·3/4H2O, 5·1/2CH2Cl2, and 7·2CH2Cl2 have been established by X-ray crystallography.

Reaction of the [Me4N]2[Cd(SPh-4-Me)4] with two equivalents of [M(PPh3)2NO3] afforded the neutral linear trinuclear complexes [Cd(μ-SPh-4-Me)4{M(PPh3)2}2] (M = Cu 1, Ag 2) in which two [M(PPh3)2]+ fragments chelate with the opposite edges of a tetrahedral [Cd(SPh-4-Me)4]2− moiety via the sulfur atoms of the Me-4-PhS− species. Treatment of [Sn(SPh)4] with two equivalents of [Ag(PPh3)2NO3] gave the neutral linear trinuclear complex [Sn(μ-SPh)6(AgPPh3)2] (3) that is composed of a central distorted SnS6 octahedron sharing two opposite planes with two slightly distorted AgS3P tetrahedrons. Complexes 2 and 3 are air and optically stable. Their nonlinear optical absorption and refraction were investigated under the same conditions. The nonlinear optical absorption and refraction of complex 2 were determined to be α2 = 3.11 × 10−11 m/W and n2 = 4.15 × 10−12 esu, respectively. The nonlinear optical absorption and refraction of complex 3 were determined to be α2 = 8.36 × 10−11 m/W and n2 = 1.47 × 10−11 esu, respectively.

ZnO nanorods were prepared via a simple hydrothermal oxidization process on zinc substrate. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrum (EDS), transmission electron microscopy (TEM) and photoluminescence (PL) spectrum were used to characterize the nanorods. The nanorods are single crystalline wurtzite structure with a length longer than 10 μm. The effects of the hydrothermal temperature, pressure and time on the morphology, diameter and length of the ZnO nanorods have been also analyzed. It is considered that time keeping the temperature and pressure is the main factor that influences the length of the ZnO nanorods. The PL spectrum shows a strong blue light emission at 439 nm, which is considered to be caused by radiative recombination of photo-generated holes with singularly ionized oxygen vacancies. The growth process of the ZnO nanorods is proposed based on the solid–liquid–solid (SLS) mechanism.

Treatment of dimeric [(η6-p-cymene)RuCl(μ-Cl)]2 with Lawesson’s reagent [ArP(S)(μ-S)]2 (Ar = p-C6H4OMe) in THF gave [(η6-p-cymene)Ru{μ-η1(S),η2(S,S′)-ArP(S)S2}]2 (1) as the sole isolable product. The chlorides in the starting ruthenium compound were substituted by [ArP(S)S2]2− as a bridging dithiolato ligand. Interactions of [Ru(PPh3)3Cl2] and [RuHCl(CO)(PPh3)3] with Lawesson’s reagent in the presence of ammonium hydroxide gave the dinuclear neutral complexes [Ru(μ-η1(O),η1(S),η1(S,S′)-ArPOS2)(PPh3)2]2 (2) and [Ru(CO)(μ-η1(O),η2(S,S′)-ArPOS2)(PPh3)]2 (3), respectively, in which the [ArPOS2]2− ligands bind the two Ru atoms via both sulfur and oxygen atoms. Reaction of dimeric [Cp*Ru(OMe)]2 (Cp* = η5-C5Me5) with Lawesson’s reagent in the presence of ammonium hydroxide led to isolation of a novel ruthenium(IV) complex, [Cp*Ru{(ArPS2O)2H}] (4). Reaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with Na[FcP(OMe)S2], which was prepared from [FcP(S)(μ-S)]2 (Fc = Fe(η5-C5H4)(η5-C5H5)) and MeONa in methanol, gave the neutral mononulcear complexes cis-[Ru{Fc(OCH3)PS2}2(L′)(PPh3)] (L′ = PPh3 5, CO 6). Interaction of [Ru(PPh3)3Cl2] or [RuHCl(CO)(PPh3)3] with [FcP(S)(μ-S)]2 in the presence of ammonium hydroxide in THF gave [Ru{Fc(OH)PS2}2(L′)(PPh3)] (L′ = PPh3 7, CO 8). Treatment of [(η6-p-cymene)RuCl(μ-Cl)]2 with [FcP(OH)S(SH)] in the presence of excess NaHCO3 led to isolation of [(η6-p-cymene)Ru{η1(S),η2(S,S′)-FcPS2OP(S)SFc}] (9). The crystal structures of 1, 2, 3·CH2Cl2·THF, 4·CH2Cl2·0.5H2O, 6, 7·CH2Cl2·3/4C6H14, and 9·CH2Cl2 along with their spectroscopic properties are reported.

The treatment of a slurry of an equimolar mixture of [Sn(edt)2] (edt = ethane-1,2- dithiolate) and [Et4N]Cl·xH2O with CuI in the presence of PPh3 gave a tetranuclear compound, [Sn(edt)2Cl(μ-I)(μ3-I)(CuPPh3)3] (1), which consists of a rectangular-pyramidal [Sn(edt)2Cl]− moiety ligated by three [Cu(PPh3)]+ fragments via the sulfur atoms of the edt2− ligands. The treatment of a slurry of [Sn(edt)2] and excess [Et4N]Br with [Cu(MeCN)4][PF6] in the presence of PPh3 afforded a pentanuclear compound, [Sn(edt)2(μ-Br)2(μ3-Br)2(CuPPh3)4] (2), which comprises two [(CuPPh3)2(μ-Br)]+ fragments symmetrically ligating an octahedral trans-[Sn(edt)2Br2]2− moiety via the sulfur and bromide atoms. Reaction of [Sn(edt)2] with [Cu(MeCN)4][PF6] and PPh3 in a mixed MeCN/CH2Cl2 solution yielded a novel octanuclear compound, [{Sn(edt)2}3(μ-OH)3Cu5(PPh3)8][PF6]2 (3), which may be described as a triangular [{Sn(edt)2}3(μ-OH)3]3− core chelated by three [Cu(PPh3)2]+ species and capped by two [Cu(PPh3)]+ species. The luminescent properties of compounds 1, 2, and 3 were investigated in a CH2Cl2 solution at room temperature. Upon excitation at λ > 360 nm, these compounds are luminescent in CH2Cl2 solution with emissions having maxima at 422, 515, and 494 nm, respectively.

Treatment of [Et4N][GaCl4] with four equivalents of NaQR in methanol afforded the substitution complexes [Et4N][Ga(QR)4] (QR = SC6H4Me-p1, QR = SePh 3), while the indium analogues [Et4N][In(SC6H4Me-p)4] (2) was prepared by the reaction of InCl3·3H2O and NaSC6H4Me-p in the presence of [Et4N]Cl·xH2O. The structures of these three complexes, as determined by single-crystal X-ray diffraction, feature well-separated cations and anions with the metal centers of the anions tetrahedrally coordinated to four thiolate or selenolate ligands. The thermal stability of the three complexes was studied by thermal gravimetric analysis.

Cadmium tellurium cluster molecule [Cd10Te4(SC6H4Me-p)12] and bifunctioanal organic ligand 4,4′-trimethylenedipyridine (tmdp) are joined together through metal–ligand coordination bonds, forming a new inorganic–organic hybrid polymeric cluster {Cd10Te4(SC6H4Me-p)12(tmdp)2}n (1) with a unique two-dimensional super-structure. The room temperature absorption and the diffuse reflectance UV–Vis spectra along with the photo-luminescence behavior were determined in the solid state. The thermal stability of the polymeric cluster was studied by thermal gravimetric analysis.A new inorganic–organic hybrid polymeric cluster {Cd10Te4(SC6H4Me-p)12(tmdp)2}n with a unique two-dimensional super-structure was solvothermally synthesized and structurally characterized.

Co-crystallization of the tetra-iso-butyl-resorcin[4]arene (1) with 1,4-bis-(pyridyl)ethane (bpe) obtained from methanol yields a molecular solid of the multicomponent host–guest complex 1 · 2(bpe) · 0.5MeOH · H2O (2) in which 1 assemblies with water molecules to form a hydrogen-bonded dimer. The bpe ligands in both cis- and trans-stereo configurations exist in the complex 2, of which trans-bpe moieties as guests are encapsulated in the capsules constructed by two pairs of opposition bowls of resorcinarenes.

Interaction of [Cp*RuCl(μ-Cl)]2 with 2,2′-bipyridine (2,2′-bipy) in the presence of Na[PF6] gave a chloride bridging dinuclear complex [{Cp*Ru(2,2′-bipy)}2(μ-Cl)][PF6] (1). In the crystal structure, the cation [{Cp*Ru(2,2′-bipy)}2(μ-Cl)]+ contains a bent Ru–Cl–Ru linkage with an angle of 141.87(12)°. The tris(μ-hydroxo)diruthenium complex [{(η6-p-cymene)Ru}2(μ-OH)3][BF4] in acetone solution was treated by 4,4′-bipyridine (4,4′-bipy) to give a hydroxo-bridged tetranuclear complex [{(η6-p-cymene)Ru}2(μ-OH)2(μ-4,4′-bipy)]2[BF4]4 (2). Complex 2 consists of four (η6-p-cymene)Ru moieties connected by two 4,4′-bipy and four hydroxo-bridging groups, forming a novel metallomacrocycle with alternating hydroxyl and 4,4′-bipy bridges between the ruthenium atoms. Spectroscopic properties along with electrochemistry of two organoruthenium (II) complexes 1 and 2 are reported.Two new cationic polynuclear organoruthenium (II) complexes are reported. Dinuclear Cp*Ru complex [{Cp*Ru(2,2′-bipy)}2(μ-Cl)][PF6] (1) contains a labile chloride ligand in the bent Ru–Cl–Ru linkage and tetranuclear (η6-p-cymene)Ru complex [{(η6-p-cymene)Ru}2(μ-OH)2(4,4′-bipy)]2[BF4]4 (2) shows a novel metallomacrocyclic structure with hydroxo bridges.

Treatment of tetraphosphonitoresorcinarene [(CH3)2CHCH2CHC6H2O2PPh]4 (1) with an excess [CuCl] powder in the presence of pyridine (py) yielded a tetracopper(I) phosphonitocavitand [pyH][1·Cu4(μ-Cl)4(μ4-Cl)] (2). The Included μ4-Cl in 2 was easily substituted by heavy halide anion to give [pyH][1·Cu4(μ-Cl)4(μ4-X)] (X=Br, 3; I, 4). The complexes 2, 3, and 4 have been characterized by X-ray structure determinations. The similar structure contains four coplanar cupper atoms bridged by four μ-Cl and one central trapped μ4-X atoms in the inside of the closing bowl-shaped cavitand. The third-order nonlinear optical properties of 2 as a typical metal-cavitand complex were investigated in this paper.

Methylresorcin[4]arenes in the C2h and C4v symmetrical chair and crown conformers, and resorcin[4]arene in the C2v symmetrical boat conformation have been synthesized from the typical one-pot acid-catalyzed reaction and structurally characterized. Solvation of organic molecules in the crystalline state of the chair and boat isomers shows inter-resorcin[4]arene interactions held together by intermolecular hydrogen bonds involving solvate molecules. The intramolecular hydrogen bonds naturally form in the crown isomer of the substituted resorcin[4]arenes.

Two sulfur-bridged carbonyl clusters [(μ-SPh)2Fe2(CO)6]2(μ4-S) 1 and [PPN][(μ3-S)2Mn3(CO)9] 2 were synthesized for study of the third-order nonlinear properties. Cluster 1 consists of two doubly bridged Fe2(CO)6 fragments bonded for a center μ4-sulfur atom of the distorted tetrahedron. Each fragments is also bridged with the sulfur from a thiophenol group. Cluster 2 exhibits a D3h equilateral triangular frame with three Mn(CO)3 units apically bicapped by the two μ3-sulfur atoms. The moderate third-order optical nonlinear absorption and refraction effects of clusters 1 and 2 in CH2Cl2 solution were observed at 532 nm by using of the z-scan measurements of an 8-ns pulsed laser. The third-order nonlinear optical susceptibilities, χ(3), were detected with 5.4×10−13 and 1.2×10−13 esu for 1 and 2, respectively, in solution. The structure–property relationship in clusters is also discussed in the paper.

A typical silver cubane-like heteroselenometallic cluster, (μ3-WSe4)Ag3(PPh3)3Cl·0.5SePPh3, was synthesized from reaction of [Et4N]2[WSe4] and Ag(PPh3)2(NO3) in CH2Cl2 solution and structurally characterized by X-ray crystallography. The compound crystallizes in the trigonal space group R3 with a=16.258(4), b=22.80(3) Å, V=5217(7) Å3, and Z=3. The structure contains a strongly distorted cubane-like {WAg3Se3Cl} core. The coordination geometries of the W center and each Ag atom are tetrahedral. The mean W–Ag separation is 3.010(3) Å. Optical nonlinearity of this cubane-like cluster was studied. Large optical limiting effect with threshold of 0.45 J/cm2 was observed with the laser pulses of 7 ns at 532 nm.

Chalcogenolate clusters can be interlinked with organic linkers into semiconducting coordination polymers with photocatalytic properties. Here, discrete clusters of Cd8S(SPh)14(DMF)3 were interlinked with 4,4′-bipyridine into a one dimensional coordination polymer of [Cd8S(SPh)14(DMF)(bpy)]n with helical chains. A stepwise mechanism for the assembly of the coordination polymer in DMF was revealed by an ex situ dynamic light scattering study. The cluster was electrostatically neutral and showed a penta-supertetrahedral structure. During the assembly each cluster was interlinked with two 4,4′-bipyridine molecules, which replaced the two terminal DMF molecules of the clusters. In their solid-state forms, the cluster and the coordination polymer were semiconductors with wide band gaps of 3.08 and 2.80 ev. They photocatalytically degraded rhodamine B and methylene blue in aqueous solutions. The moderate conditions used for the synthesis could allow for further in situ studies of the reaction-assembly of related clusters and coordination polymers.

Ternary supertetrahedral chalcogenolate clusters were interlinked with bipyridines into a microporous semiconducting framework with properties qualitatively different from those of the original clusters. Both the framework and the clusters were effective photocatalysts, and rapidly degraded the dye rhodamine B.