Kim Do-Hyeon, Koo Ja-Eung, Hong Chang Seop, Oh Sangjun, Do Youngkyu
Department of Chemistry, School of Molecular Science-BK21 and Center for Molecular Design and Synthesis, Korea Advanced Institute of Science and Technology, Daejeon 305-701, Republic of Korea.
Inorg Chem. 2005 Jun 13;44(12):4383-90. doi: 10.1021/ic048267c.
The first examples of high-dimensional mixed-valence homometallic cyano-bridged copper complexes were synthesized and characterized: net-structured Cu(CN)(4){Cu(cyclam)}(1.5)(n)()(H(2)O)(5)(n) (1), ladder-type double-chain-structured Cu(CN)(2){Cu(CN)(2)Cu(cyclam)}()(H(2)O)(n) (2), layer-structured {Cu(CN)(2)}(2)Cu(cycalm) (3), and hydrogen-bond-based 2-D Cu(CN)(3)Cu(cyclam)()(CH(3)OH)(n) (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane). (1) Crystallizes in triclinic space group P with a = 8.3589(11) A, b = 13.478(2) A, c = 14.828(2) A, alpha = 66.895(2) degrees , beta = 77.916(3) degrees , gamma = 85.939(3) degrees , and Z = 1; (2) crystallizes in triclinic space group P with a = 8.2305(12) A, b = 9.8861(15) A, c = 13.219(2) A, alpha = 84.863(3) degrees , beta = 75.744(3) degrees , gamma = 89.818(3) degrees , and Z = 2; 3 crystallizes in monoclinic space group P2(1)/c with a = 6.830(2) A, b = 8.482(2) A, c = 17.306(4) A, beta = 98.144(4) degrees , and Z = 2; 4 crystallizes in triclinic space group P with a = 9.470(1) A, b = 10.034(1) A, c = 12.064(1) A, alpha = 67.325(2), beta = 75.593(2), gamma = 70.672(2), and Z = 2. The coordination sphere of Cu(I) sites in the complexes shows diverse structures: tetrahedral [CuC(4)] for (1), tetrahedral [CuC(3)N] and triangular [CuC(2)N] for (2), triangular [CuC(2)N] for (3), and triangular [CuC(3)] for 4. In particular, (1) constitutes the first example of a structurally characterized system containing a bridging tetrahedral Cu(CN)(4)(-) unit. The diverse structural nature of these complexes is governed by the capping amines and the content of water in the reaction media. The magnetic interactions are negligible in these mixed-valence complexes.
网状结构的Cu(CN)(4){Cu(环胺)}(1.5)(n)()(H(2)O)(5)(n) (1)、梯型双链结构的Cu(CN)(2){Cu(CN)(2)Cu(环胺)}()(H(2)O)(n) (2)、层状结构的{Cu(CN)(2)}(2)Cu(环胺) (3)以及基于氢键的二维Cu(CN)(3)Cu(环胺)()(CH(3)OH)(n) (4)（环胺 = 1,4,8,11 - 四氮杂环十四烷）。(1) 结晶于三斜空间群P，a = 8.3589(11) Å，b = 13.478(2) Å，c = 14.828(2) Å，α = 66.895(2)°，β = 77.916(3)°，γ = 85.939(3)°，Z = 1；(2) 结晶于三斜空间群P，a = 8.2305(12) Å，b = 9.8861(15) Å，c = 13.219(2) Å，α = 84.863(3)°，β = 75.744(3)°，γ = 89.818(3)°，Z = 2；3结晶于单斜空间群P2(1)/c，a = 6.830(2) Å，b = 8.482(2) Å，c = 17.306(4) Å，β = 98.144(4)°，Z = 2；4结晶于三斜空间群P，a = 9.470(1) Å，b = 10.034(1) Å，c = 12.064(1) Å，α = 67.325(2)，β = 75.593(2)，γ = 70.672(2)，Z = 2。配合物中Cu(I)位点的配位球呈现出多样的结构：(1) 为四面体[CuC(4)]，(2) 为四面体[CuC(3)N]和三角形[CuC(2)N]，(3) 为三角形[CuC(2)N]，4为三角形[CuC(3)]。特别地，(1) 构成了首个结构表征的含有桥连四面体Cu(CN)(4)(-)单元的体系实例。这些配合物多样的结构性质受封端胺和反应介质中水的含量的控制。在这些混合价态配合物中，磁相互作用可忽略不计。
