Reactions of the preformed cluster precursor [Et4N]2[Mo2S2(μ-S)2(edt)2] (edt = ethanedithiolate) (1) with [Au(PPh3)Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4(AuPPh3)...Reactions of the preformed cluster precursor [Et4N]2[Mo2S2(μ-S)2(edt)2] (edt = ethanedithiolate) (1) with [Au(PPh3)Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4(AuPPh3)(edt)2]·0.25Et2O·0.25MeOH (2·0.25Et2O·0.25MeOH). It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117(4), b = 9.2705(19), c = 44.418(9) A^°, β= 93.19(3)°, V = 8271(3) A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F(000) = 4380, μ(MoKa) = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ(I). The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^+ cation is coordinated by one bridging S and two terminal S atoms of the [(edt)2Mo2(S)2(μ-S)2] moiety. The Au(I) center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425(2) to 2.898(3)A^°.展开更多
The multivariate statistical analysis is profitably applicable to the study of conodont multielement taxonomy.R- mode duster analyses of quantitative and 0-1 data are carried out here to classify more than 6000 discre...The multivariate statistical analysis is profitably applicable to the study of conodont multielement taxonomy.R- mode duster analyses of quantitative and 0-1 data are carried out here to classify more than 6000 discrete Lower Triassic conodont specimens belonging to 108 kinds of conodont elements from Western Guangxi . The results of R-mode cluster analysis reveal more directly the relationship among many isolated conodont elements , and they also prove that the results of the logical inference are basically correct,i.e. 108 kinds of conodont elements can be identified into 32 species belonging to 11 genera of conodonts . The application of R- mode duster analysis multielement taxonomy by the method . has brought about 4 significant conclusions , which can be used by conodont researchers as reference .展开更多
A series of tetrahedral iridium carbonyl clusters coordinated by systematically varied series of ligands have been studied by TDDFT method focusing on their electronic and non- linear optical properties. The clusters ...A series of tetrahedral iridium carbonyl clusters coordinated by systematically varied series of ligands have been studied by TDDFT method focusing on their electronic and non- linear optical properties. The clusters of Ir4(CO)12 (1), Ir4(μ-CO)3(CO)9 (2), Ir4(μ-L)(CO)10 (L = dppm 3, dppe 4, (Ph2P)2CHMe 5, Ph2P(CH2)3PPh2 6) and Ir4(CO)10(phen) (phen = 1,10-phen- anthroline) (7) exhibit the first static hyperpolarizabilities of medium magnitude (βtot-10×10^-30 esu). The second order nonlinear optical response of the seven clusters increase from 0 to 23 ×10^-30 esu; the high symmetric cluster Ir4(CO)12 debases its symmetry and presents the second order nonlinear optical behavior as the coordination style of some carbonyls changes to bridge style, and then the response increases regularly with the systematical variation of the ligands. The origination of the first hyperpolarizability is discussed by the expanded orbital decomposition scheme. The results suggest the d-d electron transition from the apical iridium atom to the other three Ir atoms inside the metal skeleton, and d-πelectron transitions from metals to carbonyls are responsible for the first hyperpolarizabilities. Particularly, for cluster 7, the charge transfer from d orbitals of iridium to π* orbirals of phenanthroline originates the first hyperpolarizabilities.展开更多
Three new cadmium or zinc arenedisulfonate complexes [Zn(bpp)2(L)]n 1, { [Cd(bpp)2(1,5-NDS)(H2O)2]·4H2O }n 2 and { [Cd(bpp)2(H2O2)2]·(1,5-NDS) } n 3 (L = 4,4′-bis(2-sulfonatostyryl)biphen...Three new cadmium or zinc arenedisulfonate complexes [Zn(bpp)2(L)]n 1, { [Cd(bpp)2(1,5-NDS)(H2O)2]·4H2O }n 2 and { [Cd(bpp)2(H2O2)2]·(1,5-NDS) } n 3 (L = 4,4′-bis(2-sulfonatostyryl)biphenyl, bpp = 1,3-di(4-pyd-dyl)propane and 1,5-NDS = 1,5-Naphthalenedisulfonate) have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1: space group P21/n, a = 10.559(3), b = 13.138(4), c = 17.623(5)A^°, β = 100.852(3)°, V = 2400.9(12) A^°^3 Z = 2, Dc= 1.351 g/cm^3, F(000) = 1016, μ = 0.654 mm^-1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2: space group P^-1, a = 8.5642(19), b = 10.076(3), c = 12.114(3) A^°, α = 81.623(7), β = 77.149(8), γ = 82.787(7)°, V = 1003.6(4) A^°^3 Z = 1, Dc= 1.495 g/cm^3, F(000) = 466,μ = 0.713 mm^3, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3: space group C2/c, a = 21.6024(15), b = 9.4608(5), c = 18.4656(11)A^°, β = 107.359(3)°, V= 3602.0(4)A^°^3 Z = 4, Dc= 1.533 g/cm^3, F(000) = 1704,μ = 0.780 mm^-1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn(bpp)2^2+ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1-3 display photoluminescent emissions at 452 and 335 nm, respectively.展开更多
基金supported by the National Natural Science Foundation of China (No. 20525101 and 20871088)the "SooChow Scholar" Program and Program for Innovative Research Team of Suzhou University
文摘Reactions of the preformed cluster precursor [Et4N]2[Mo2S2(μ-S)2(edt)2] (edt = ethanedithiolate) (1) with [Au(PPh3)Cl] in MeOH/MeCN gave rise to a new heterobimetallic Mo/Au/S cluster [Et4N][Mo2S4(AuPPh3)(edt)2]·0.25Et2O·0.25MeOH (2·0.25Et2O·0.25MeOH). It was characterized by elemental analysis, IR spectrum and X-ray analysis. 2·0.25Et2O·0.25MeOH crystallizes in the monoclinic system, space group C2/c with a = 20.117(4), b = 9.2705(19), c = 44.418(9) A^°, β= 93.19(3)°, V = 8271(3) A^°^3, Z = 8, Dc = 1.794 g/cm^3, T = 193 K, C31.25H43AuMo2NO0.50PS8, Mr = 1116.96, F(000) = 4380, μ(MoKa) = 4.603 mm^-1, S = 1.019, R = 0.0672 and wR = 0.1708 for 7243 observed reflections with I 〉 2σ(I). The anion of 2 consists of a butterfly-shaped Mo2S4Au core in which one [AuPPh3]^+ cation is coordinated by one bridging S and two terminal S atoms of the [(edt)2Mo2(S)2(μ-S)2] moiety. The Au(I) center adopts a pseudo-tetrahedral coordination geometry, and the Au-S bond lengths vary from 2.425(2) to 2.898(3)A^°.
文摘The multivariate statistical analysis is profitably applicable to the study of conodont multielement taxonomy.R- mode duster analyses of quantitative and 0-1 data are carried out here to classify more than 6000 discrete Lower Triassic conodont specimens belonging to 108 kinds of conodont elements from Western Guangxi . The results of R-mode cluster analysis reveal more directly the relationship among many isolated conodont elements , and they also prove that the results of the logical inference are basically correct,i.e. 108 kinds of conodont elements can be identified into 32 species belonging to 11 genera of conodonts . The application of R- mode duster analysis multielement taxonomy by the method . has brought about 4 significant conclusions , which can be used by conodont researchers as reference .
基金Supported by the National Natural Science Foundation of China (20573114)the MOST (2006DFA43020)Natural Science Foundation of Fujian Province (2006F3133 and 13071062)
文摘A series of tetrahedral iridium carbonyl clusters coordinated by systematically varied series of ligands have been studied by TDDFT method focusing on their electronic and non- linear optical properties. The clusters of Ir4(CO)12 (1), Ir4(μ-CO)3(CO)9 (2), Ir4(μ-L)(CO)10 (L = dppm 3, dppe 4, (Ph2P)2CHMe 5, Ph2P(CH2)3PPh2 6) and Ir4(CO)10(phen) (phen = 1,10-phen- anthroline) (7) exhibit the first static hyperpolarizabilities of medium magnitude (βtot-10×10^-30 esu). The second order nonlinear optical response of the seven clusters increase from 0 to 23 ×10^-30 esu; the high symmetric cluster Ir4(CO)12 debases its symmetry and presents the second order nonlinear optical behavior as the coordination style of some carbonyls changes to bridge style, and then the response increases regularly with the systematical variation of the ligands. The origination of the first hyperpolarizability is discussed by the expanded orbital decomposition scheme. The results suggest the d-d electron transition from the apical iridium atom to the other three Ir atoms inside the metal skeleton, and d-πelectron transitions from metals to carbonyls are responsible for the first hyperpolarizabilities. Particularly, for cluster 7, the charge transfer from d orbitals of iridium to π* orbirals of phenanthroline originates the first hyperpolarizabilities.
基金supported by the State Key Laboratory of Structural Chemistry (CAS, SZD08002-2)National Basic Research Program of China (973 Program, 2007CB815306)the National Natural Science Foundation of China (20733003, 20673117)
文摘Three new cadmium or zinc arenedisulfonate complexes [Zn(bpp)2(L)]n 1, { [Cd(bpp)2(1,5-NDS)(H2O)2]·4H2O }n 2 and { [Cd(bpp)2(H2O2)2]·(1,5-NDS) } n 3 (L = 4,4′-bis(2-sulfonatostyryl)biphenyl, bpp = 1,3-di(4-pyd-dyl)propane and 1,5-NDS = 1,5-Naphthalenedisulfonate) have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1: space group P21/n, a = 10.559(3), b = 13.138(4), c = 17.623(5)A^°, β = 100.852(3)°, V = 2400.9(12) A^°^3 Z = 2, Dc= 1.351 g/cm^3, F(000) = 1016, μ = 0.654 mm^-1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2: space group P^-1, a = 8.5642(19), b = 10.076(3), c = 12.114(3) A^°, α = 81.623(7), β = 77.149(8), γ = 82.787(7)°, V = 1003.6(4) A^°^3 Z = 1, Dc= 1.495 g/cm^3, F(000) = 466,μ = 0.713 mm^3, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3: space group C2/c, a = 21.6024(15), b = 9.4608(5), c = 18.4656(11)A^°, β = 107.359(3)°, V= 3602.0(4)A^°^3 Z = 4, Dc= 1.533 g/cm^3, F(000) = 1704,μ = 0.780 mm^-1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn(bpp)2^2+ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1-3 display photoluminescent emissions at 452 and 335 nm, respectively.