A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has bee...A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.展开更多
Two new complexes, [W2Ag2S8?Ca(DMF)6]n 1 and [WAgS4?Na(DMF)3]n 2, have been synthesized and characterized. Single-crystal X-ray analyses show both 1 and 2 have {WAgS4}n anion linear chains, but 1 has a discrete [Ca(DM...Two new complexes, [W2Ag2S8?Ca(DMF)6]n 1 and [WAgS4?Na(DMF)3]n 2, have been synthesized and characterized. Single-crystal X-ray analyses show both 1 and 2 have {WAgS4}n anion linear chains, but 1 has a discrete [Ca(DMF)6]2+ cation while 2 is a linear chain. UV-Visible-Near-IR spectroscopy data show that the bandgaps of the two complexes are 1.86 and 1.99 eV, respectively. Electrical conductivity measurements reveal the conductivities of 1 and 2 are 10?7 and 10?8 Scm?1, respectively and they exhibit thermally activated temperature depen- dence, which may be attributed to semiconductors.展开更多
The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3....The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3. The structure contains a [W2CuAgS4](4+) distorted cubane-like core, Two types of metal-metal bonds exist in the core, One is W-W bond of which length is 0.2871(1) nm, the other is W-M' (M'=Cu or Ag) bends, whose mean distance is 0.2980 nm. The details of synthesis, structure, IR, UV-Vis and P-31 NMR spectra are reported. The crystallographic data are: space group P2(1)/n, with a=1.6987(4), b=1.7763(6), c=1.8918(5) nm, beta=98.54(2)degrees, V=5.645(3) nm(3), Z=4, and final R=0.043 for 6437 observed reflections.展开更多
文摘A new heterometallic cluster W2Ag2S4(tdt)2(PPh3)2·CH2Cl2(H2tdt=H2CH3C6H3S2)(Ⅱ) has been prepared from the reaction of a well-defined molecular building block W2S4(tdt)22-(I) with Ag complex. The compound has been characterized by X-ray diffraction study, IR., UV-Vis Spectroscopy and cyclic voltammetry.Crystallographic data for the compound are: space group P21/n,a=17.234(4), b=17.622(4), c=19. 094(4) A,β= 99. 22(2)°,V=5704(2) A3, Z=4,final R=0. 042 and Rw=0. 049 for 5983 independent reflections with I≥3σ(I) The structure analysis reveals that the cluster contains a cubane-like core [W2Ag2S4]4+ . The coordination geometry of each tungsten atom is a square pyramid just as that in the building block. Two types of metal-metal bonds of W-W bond and W-Ag bond exist in the core. The distance between two Ag atoms is out of the range of bonding.
基金This research was supported by the State Key Laboratory of Structural Chemistry, the National Science and Technology of China (001CB1089), the Chinese Academy of Sciences (CAS), the National Science Foundation of China (20273073, 20333070, 90206040)
文摘Two new complexes, [W2Ag2S8?Ca(DMF)6]n 1 and [WAgS4?Na(DMF)3]n 2, have been synthesized and characterized. Single-crystal X-ray analyses show both 1 and 2 have {WAgS4}n anion linear chains, but 1 has a discrete [Ca(DMF)6]2+ cation while 2 is a linear chain. UV-Visible-Near-IR spectroscopy data show that the bandgaps of the two complexes are 1.86 and 1.99 eV, respectively. Electrical conductivity measurements reveal the conductivities of 1 and 2 are 10?7 and 10?8 Scm?1, respectively and they exhibit thermally activated temperature depen- dence, which may be attributed to semiconductors.
基金Project supported by the National Natural Science Foundation of China and the Foundation of the State Key Laboratory of Structural Chemistry.
文摘The trimetallic cluster W2CuAgS4(TDT)(2)(PPh3)(2) . CH2Cl2 (TDT=[S-2(C6H3)CH3](2-)) (2) has been prepared from the reaction of the well-defined molecule building block [W2S4(TDT)(2)](2-) (1) with AgNO3, CuBr and PPh3. The structure contains a [W2CuAgS4](4+) distorted cubane-like core, Two types of metal-metal bonds exist in the core, One is W-W bond of which length is 0.2871(1) nm, the other is W-M' (M'=Cu or Ag) bends, whose mean distance is 0.2980 nm. The details of synthesis, structure, IR, UV-Vis and P-31 NMR spectra are reported. The crystallographic data are: space group P2(1)/n, with a=1.6987(4), b=1.7763(6), c=1.8918(5) nm, beta=98.54(2)degrees, V=5.645(3) nm(3), Z=4, and final R=0.043 for 6437 observed reflections.
