Novel Examples of High-Dimensional Mixed-Valence Copper Cyanide Complexes

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]2n(H2O)5n (1), ladder-type double-chain-structured [Cu(CN)2{Cu(CN)2Cu(cyclam)}]n(H2O)n (2), layer-structured [{Cu(CN)2}2Cu(cycalm)]n (3), and hydrogen-bond-based 2-D [Cu(CN)3Cu(cyclam)]n(CH3OH)n (4) (cyclam = 1,4,8,11-tetraazacyclotetradecane). 1 crystallizes
in triclinic space group P1̄ with 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)°, and Z = 1; 2 crystallizes in triclinic space group P1̄ with 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)°, and Z = 2; 3 crystallizes in
monoclinic space group P21/c with a = 6.830(2) Å, b = 8.482(2) Å, c = 17.306(4) Å, β = 98.144(4)°, and Z =
2; 4 crystallizes in triclinic space group P1̄ with 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), and Z = 2. The coordination sphere of CuI sites in the complexes shows diverse
structures:  tetrahedral [CuC4] for 1, tetrahedral [CuC3N] and triangular [CuC2N] for 2, triangular [CuC2N] for 3, and
triangular [CuC3] for 4. In particular, 1 constitutes the first example of a structurally characterized system containing
a bridging tetrahedral [Cu(CN)4]3- 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.

本研究首次合成并表征了高维混合价同金属氰基桥联铜配合物：分别为网状结构的[Cu(CN)4{Cu(cyclam)}1.5]2n(H2O)5n (1)、梯状双链结构的[Cu(CN)2{Cu(CN)2Cu(cyclam)}]n(H2O)n (2)、层状结构的[{Cu(CN)2}2Cu(cyclam)]n (3)，以及基于氢键的二维[Cu(CN)3Cu(cyclam)]n(CH3OH)n (4)（其中cyclam为1,4,8,11-四氮杂环十四烷，英文全称为1,4,8,11-tetraazacyclotetradecane）。化合物1于三斜晶系P1̄空间群中结晶，晶胞参数为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值为1；化合物2于三斜晶系P1̄空间群中结晶，晶胞参数为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值为2；化合物3于单斜晶系P21/c空间群中结晶，晶胞参数为a=6.830(2) Å，b=8.482(2) Å，c=17.306(4) Å，β=98.144(4)°，Z值为2；化合物4于三斜晶系P1̄空间群中结晶，晶胞参数为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值为2。上述配合物中一价铜（CuI）位点的配位环境呈现多样构型：化合物1为四面体构型[CuC4]，化合物2包含四面体构型[CuC3N]与三角锥形[CuC2N]，化合物3为三角锥形[CuC2N]，化合物4为三角锥形[CuC3]。尤为特别的是，化合物1是首个被结构解析并表征的包含桥联四面体[Cu(CN)4]3-单元的体系。此类配合物的结构多样性由封端胺类配体与反应介质中的水含量共同调控。此外，这类混合价配合物的磁相互作用可忽略不计。