Self-assembly of a Mixed-valence Cu(Ⅰ)/Cu(Ⅱ)Coordination Polymer Derived from a Conformationally Flexible Tripodal Phosphoric Trimide Ligand  

作　　者：弓亚琼 高金伟 米陶清 

机构地区：[1]Industry and Ecology Institute, North University of China [2]State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences

出　　处：《Chinese Journal of Structural Chemistry》2016年第5期747-752,共6页结构化学（英文）

基　　金：supported by the Natural Science Foundation of Shanxi province(2012021005-2);Technology Foundation for Selected Overseas of Shanxi

摘　　要：Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.Reaction of a tripodal ligand, N,N＇,N＇＇-tris（3-pyridinyl） phosphoric trimide（TPPA） and CuBr_2·2H_2O result in the assembly of a new polymeric copper coordination polymer, which was characterized by single-crystal diffraction, infrared spectroscopy and elemental analysis. The polymer crystallizes in the triclinic system, space group P1 with a = 9.0964（5）, b = 10.2592, c = 10.5822（8） A, V = 933.01（9） A3, Z = 2, C_（30）H_（24）Br_4Cu_3N_（12）O_2P_2, M_r = 985.02, D_c = 1.753 g/cm3, F（000） = 4072 and μ（MoKα） = 0.746 mm^（-1）. The final R and w R are 0.0588 and 0.1329 for 4260 observed reflections with I 〉 2σ（I）. Cu（Ⅰ） is tetrahedrally coordinated and Cu（Ⅱ） center adopts square planar coordination geometry. Because of the flexibility of the TPPA ligands, the pyridyl rings rotate though a certain angle and three pyridyl rings on the same TPPA rotate by about 45° with respect to the central P=O groups. TPPA ligand acts as a tridentate ligand and is coordinated with three metal centers with its pyridyl donors to form a 2D-sheet like structure, and it is further connected by N-H···O and N-H···Br, resulting in a 3D network packing. Oxidation states of the metal center have been determined by bond valence sum calculation.

关 键 词：copper phosphoric trimide mixed-valence complex crystal structure 

分 类 号：O641.4[理学—物理化学]