The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. ...The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.展开更多
The crystal and molecular structure of copper(Ⅱ) dimeric complex of S-methyl-B-N-(pyridine N-oxide-2-ylmethylidene) dithiocarbazate with acetonitrile, [CuL (CH3CN)]2 (ClO4)2, was determined by X-ray diffraction. The ...The crystal and molecular structure of copper(Ⅱ) dimeric complex of S-methyl-B-N-(pyridine N-oxide-2-ylmethylidene) dithiocarbazate with acetonitrile, [CuL (CH3CN)]2 (ClO4)2, was determined by X-ray diffraction. The complex crystalizes in monoclinic system with space group P21/n, a= 7. 685(2), 6=20.160(6), c= 10. 847(5) A ,B = 107.89(3), Z=2,Dc=1.788 g/cm3, F(000) = 835. 8, u= 18. 17 cm-1(Moka,R= 0. 057.Each Cu(Ⅱ) ion in the complex is surrounded by a distorted square pyramidal. The basal plane is comprised of S, N and O atoms of one ligand together with a N atom of the solvent--acetonitrile, while the axial position is occupied by the S atom of the other ligand. The bond length of Cu-S(bridging) is 3. 038A . and Cu-Cu distance is 3. 700A.展开更多
Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A= Ph_4P^+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared by the reaction of anhydrous VCl_3 and Na_2mp in the...Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A= Ph_4P^+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared by the reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N^+,L=L'= MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com- plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti- bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V= 2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono- clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8, and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)3]^(2-) fragments linked by sodium ions through the μ_3-O bridges with a crystallographic center of symmetry.The V(IV) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.展开更多
基金supported by the National Basic Research Program of China (No. 2013CB934200)National Basic Research Program of China (No. 2012CB933001)+1 种基金The Chinese Academy of Sciences (No. YZ201318)the National Natural Science Foundation of China (Nos. 21472029, 51173031, 91127043, 51203030, 51463002)
文摘The formation of coordinated dimeric complexes bridged by axial ligands on surface is observed with the help of a 1,3,5-tris（10-carboxydecyloxy）benzene（TCDB） template through scanning tunneling microscopy（STM）. STM images of molecular adlayers of zinc tetraphenylporphyrin（Zn TPP）, zinc phthalocyanine（Zn Pc）, and their mixture are reported. Zn TPP and Zn Pc can spontaneously form highly an ordered structure with a 1：1 molar ratio, which is different from that of individual Zn Pc. The coordinated bimolecular complexes bridged with axial ligands, simply as Zn Pc–DPP–Zn TPP and Zn Pc–DPE–Zn Pc, are presented and the corresponding surface structures are compared. Zn Pc and Zn TPP can be connected by an axial ligand DPP and formed assembled structures out of surface. Two types of arrays with entirely new structure are obtained for the Zn Pc–DPE–Zn Pc complex. These bridged hybrid complexes provide an example of design of self-organized crystals on the basis of coordination through non-covalent interactions.
文摘The crystal and molecular structure of copper(Ⅱ) dimeric complex of S-methyl-B-N-(pyridine N-oxide-2-ylmethylidene) dithiocarbazate with acetonitrile, [CuL (CH3CN)]2 (ClO4)2, was determined by X-ray diffraction. The complex crystalizes in monoclinic system with space group P21/n, a= 7. 685(2), 6=20.160(6), c= 10. 847(5) A ,B = 107.89(3), Z=2,Dc=1.788 g/cm3, F(000) = 835. 8, u= 18. 17 cm-1(Moka,R= 0. 057.Each Cu(Ⅱ) ion in the complex is surrounded by a distorted square pyramidal. The basal plane is comprised of S, N and O atoms of one ligand together with a N atom of the solvent--acetonitrile, while the axial position is occupied by the S atom of the other ligand. The bond length of Cu-S(bridging) is 3. 038A . and Cu-Cu distance is 3. 700A.
基金Project supported by the National Natural Science Foundation of China,the Natural Science Foundation of Chinese Academy of Sciences and the Natural Science Foundation of Fujian
文摘Tris[o-mercaptophenolato]vanadium(IV)dimer complexes(A)_2[V(mp)_3NaLL']_2(A= Ph_4P^+,H_2mp=o-mercaptophenol,L=MeCN,L'=EtOH,(1);L'=MeOH,(2))were prepared by the reaction of anhydrous VCl_3 and Na_2mp in the molar ratio 1:3.Complex(3)(A=Et,N^+,L=L'= MeOH)was prepared by the reaction of VCl_3,Na_2mp and Li_2S in the molar ratio 1:2:1.The com- plexes were characterized by X-ray diffraction crystallography,infrared spectra,magnetic suseepti- bility,and cyclic voltammetric measurements.Complex 2 crystallizes in the triclinic space group P1 with a=12.813(6),b=14.199(4),c=12.790(5),α=112.72(2),β=104.24(4).γ=88.68(4)°,V= 2073.6,and Z=1.The structure was refined to R=0.058.Complex 3 crystallizes in the mono- clinic space group P2_1/n with a=12.359(3),b=17.452(6),c=14.829(13),β=96.51(5)°,V=3177.8, and Z=2.The final R factor is 0.067.Both of the anions of 2 and 3 contain two[V(rap)3]^(2-) fragments linked by sodium ions through the μ_3-O bridges with a crystallographic center of symmetry.The V(IV) atom is in a coordination environment intermediate between a trigonal prism and an ideal octahedron.
