Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of...Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a（4,4） topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3（C3N3S3H1.5）2]（2） have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.展开更多
The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen at...The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen atmosphere using standard Schlenk techniques. It gives rise to a novel 1D polymeric compound 1 with solvent MeCN coordinated to the copper atom. This situation is unprecedented in the W(Mo)/Cu/S system. The crystals were characterized by elemental analysis, IR and single-crystal X-ray crystallography. The configuration of the polymeric compound can be viewed as a helical chain which is propagated along the crystallographic c axis. The excited state absorption and refraction of compound 1 in CH3CN solution were studied by using the Z-scan technique with laser pulses of 40 ps pulse-width at a wavelength of 532 nm. The polymeric compound possesses an optical self-focusing performance. The positive nonlinear refraction is attributed to population transitions between singlet states. Compound 1 displays a strong excited-state absorption.展开更多
The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = M...The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.展开更多
This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<...This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.展开更多
Treatment of a W/Cu/S precursor[Et_(4)N][Tp*WS_(3)(CuBr)_(3)](1)with three equiv.of CuCN in DMF/MeCN/benzonitrile(or α-tolunitrile)yielded two[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)]-based coordination polymers,[Tp*WS_(3)Cu_(3)...Treatment of a W/Cu/S precursor[Et_(4)N][Tp*WS_(3)(CuBr)_(3)](1)with three equiv.of CuCN in DMF/MeCN/benzonitrile(or α-tolunitrile)yielded two[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)]-based coordination polymers,[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)(CN)_(3)Cu]_(2)•2DMF(2•2DMF)and[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)(CN)_(3)Cu(α-tolunitrile)]_(2)•3MeCN(3•3MeCN),respectively.Structural analysis revealed that 2 adopts a 2D network with a 4.8^(2) topology while 3 has a 1D ladder-type chain.The third-order nonlinear optical responses of 2 and 3 in DMF were 10 times enhanced compared to those of the precursor cluster 1.展开更多
Reactions of (NH4)2MS4, AgBr and CuBr in r-methylpyridine produced one new compound, [MS4Cu4(r-MePy)8]M6O19] (1, M = W; 2, M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orth...Reactions of (NH4)2MS4, AgBr and CuBr in r-methylpyridine produced one new compound, [MS4Cu4(r-MePy)8]M6O19] (1, M = W; 2, M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4),b= 16.732(2), c = 28.657(7) A, V = 7400.8(8) A3, Z = 4, R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotnngstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS42- core are coordinated by four copper atoms, giving a WS4Cu4 aggregate of approximate D2h symmetry. The differences between the reaction of Cu+ with MS42- and that of Ag+ with MS42- in pyridine and its derivatives are discussed.展开更多
By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2 Cu2 S4 (TDT)2-(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (P...By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2 Cu2 S4 (TDT)2-(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (PPh3 )2 · 0. 5CH3 CH2 OH·0. 5H2O (2) have been prepared and characterized by IR, UV-Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X-ray structure analysis. Both compounds crystallize in space group P 21/ n with lattice parameters a = 1.0956(3), b = 2. 2072(3), c =2.4340(3) nm, β=100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9), b = 2.2135(3), c = 2.4317(4) nm, β = 99. 63(8)°, V = 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane-like cluster core [M2Cu2S4] (M= Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third-order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four-wave mixing (DFWM) for the first time and these clusters exhibited relatively large nonlinear optical coefficients.展开更多
基金supported by the State Key Laboratory of Structural Chemistry (CAS,SZD08002-2)National Basic Research Program of China (973 Program,2007CB815306)+2 种基金the National Natural Science Foundation of China (20903096,20733003)Young Scientist’s Foundation of Fujian Province (2006F3163)Knowledge Innovation Program of the Chinese Academy of Sciences
文摘Solvothermal reaction of [WS4]2-with CuCN and trithiocyanuric acid（L1） in orga-nic solvents gave rise to a new W/Cu/S polymer with a 2D anionic network,namely [Et4N]2[WS4Cu3（C3N3S3H1.5）2]（1）.The anionic layer of 1 is constructed by the T-shaped {WS4Cu3} subunits as nodes and L1 as linkers and features a（4,4） topology.Both 1 and its isomorphous compound [Et4N]2[MoS4Cu3（C3N3S3H1.5）2]（2） have been fully characterized by X-ray crystal analysis,IR and microanalyses.Compounds 1 and 2 show optical transitions with band gaps of 2.17 and 1.84 eV,respectively.
基金Project (2005038557) supported by the Post-Doctor Programs Foundation of Ministry of Education of China
文摘The polymeric chalcogenide [W2O2S6Cu4(NCMe)4]n (compound 1) was synthesized by the self-assembly reaction of (NH4)2(WOS3) with CuBr in MeCN in the presence of tricyclohexylphosphane (PCy3) under a purified nitrogen atmosphere using standard Schlenk techniques. It gives rise to a novel 1D polymeric compound 1 with solvent MeCN coordinated to the copper atom. This situation is unprecedented in the W(Mo)/Cu/S system. The crystals were characterized by elemental analysis, IR and single-crystal X-ray crystallography. The configuration of the polymeric compound can be viewed as a helical chain which is propagated along the crystallographic c axis. The excited state absorption and refraction of compound 1 in CH3CN solution were studied by using the Z-scan technique with laser pulses of 40 ps pulse-width at a wavelength of 532 nm. The polymeric compound possesses an optical self-focusing performance. The positive nonlinear refraction is attributed to population transitions between singlet states. Compound 1 displays a strong excited-state absorption.
基金supported by CAS (SZD08002-2)973 Program (2007CB815306)+1 种基金the NNSFC (20733003 and 20673117)the Young Scientist’s Foundation of Fujian Province (2006F3136)
文摘The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.
文摘This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.
基金the National Natural Science Foundation of China(Nos.21373142 and 21371126)the Qin-Lan Project and the“333”Project of Jiangsu Province(No.BRA2012139)the Priority Academic Program Development of Jiangsu Higher Education Institutions,and the“SooChow Scholar”Program of Soochow University.
文摘Treatment of a W/Cu/S precursor[Et_(4)N][Tp*WS_(3)(CuBr)_(3)](1)with three equiv.of CuCN in DMF/MeCN/benzonitrile(or α-tolunitrile)yielded two[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)]-based coordination polymers,[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)(CN)_(3)Cu]_(2)•2DMF(2•2DMF)and[Tp*WS_(3)Cu_(3)(μ_(3)-DMF)(CN)_(3)Cu(α-tolunitrile)]_(2)•3MeCN(3•3MeCN),respectively.Structural analysis revealed that 2 adopts a 2D network with a 4.8^(2) topology while 3 has a 1D ladder-type chain.The third-order nonlinear optical responses of 2 and 3 in DMF were 10 times enhanced compared to those of the precursor cluster 1.
文摘Reactions of (NH4)2MS4, AgBr and CuBr in r-methylpyridine produced one new compound, [MS4Cu4(r-MePy)8]M6O19] (1, M = W; 2, M = Mo), of which 1 was characterized by single crystal X-ray analysis. The crystal data: orthorhombic, Pbcn, a = 15.434(4),b= 16.732(2), c = 28.657(7) A, V = 7400.8(8) A3, Z = 4, R = 0.072 for 3121 independent data. The compound is the first example which contains both polyoxotnngstate anion and heteropolynuclear cluster cation. In the structure of the cation four edges of the tetrahedral WS42- core are coordinated by four copper atoms, giving a WS4Cu4 aggregate of approximate D2h symmetry. The differences between the reaction of Cu+ with MS42- and that of Ag+ with MS42- in pyridine and its derivatives are discussed.
基金Project (No.29733090 and 29673046) supported by the National Natural Science Foundation of Chinathe Natural Science Foundation of Fujian Province,the Foundation of State Key Laboratory of Structural Chemistry.
文摘By the additional reaction of binuclear compounds (Me4N)2M2S4 (TDT)2 (M = Mo, W; H2TDT= H2CH3GH3S2) with mononuclear cuprous complex, two new M-Cu-S clusters Mo2 Cu2 S4 (TDT)2-(PPh3)2CH3CH2OH (1) and W2Cu2S4 (TDT)2 (PPh3 )2 · 0. 5CH3 CH2 OH·0. 5H2O (2) have been prepared and characterized by IR, UV-Vis, 31P NMR spectroscopy, cyclic voltammetry and single crystal X-ray structure analysis. Both compounds crystallize in space group P 21/ n with lattice parameters a = 1.0956(3), b = 2. 2072(3), c =2.4340(3) nm, β=100.36(2)°, V= 5.790(3) nm3 and Z = 4 for 1 and a = 1.0965(9), b = 2.2135(3), c = 2.4317(4) nm, β = 99. 63(8)°, V = 5.819(8) nm3 and Z = 4 for 2. Both molecular structures contain a cubane-like cluster core [M2Cu2S4] (M= Mo, W) and their skeletons are almost the same except for M atoms. The syntheses, structures and spectrum characterizations of these two clusters are discussed. The third-order nonlinear optical (NLO) property of the two clusters was studied by the technique of forward degenerate four-wave mixing (DFWM) for the first time and these clusters exhibited relatively large nonlinear optical coefficients.
