Munakata Megumu, Ning Gui Ling, Kuroda-Sowa Takayoshi, Maekawa Masahiko, Suenaga Yusaku, Horino Takashi
Department of Chemistry and Research Institute for Science and Technology, Kinki University, Kowakae, Higashi-Osaka, Osaka 577-8502, Japan.
Inorg Chem. 1998 Oct 19;37(21):5651-5656. doi: 10.1021/ic980427v.
This paper describes two copper(I) supramolecules with the same anion and cation but quite different topologies and properties. The reaction of [Cu(CH(3)CN)(4)]PF(6) and 1,2,4,5-tetracyanobenzene (TCNB) leads to two novel polymeric coordination compounds, Cu(2)(TCNB)(3)(2)(Me(2)CO)(4)( )()(1) and Cu(2)(TCNB)(3)(2) (2), depending on the solvents used. The crystal structures have been determined by single-crystal X-ray diffraction. Crystal data are as follows. 1: C(21)H(15)N(6)O(2)CuPF(6), monoclinic, P2(1)/a, a = 11.553(4) Å, b = 16.135(7) Å, c = 15.046(3) Å, beta = 108.08(2) degrees, Z = 4. 2: C(15)H(3)N(6)CuPF(6), orthorhombic, Cmcm, a = 28.282(3) Å, b = 10.337(3) Å, c = 16.285(4) Å, Z = 16. In both polymers, copper(I) ions have similar pseudotetrahedral environments and the four coordination sites are fully occupied by the four bridging ligands, two &mgr;(2)-TCNB and two &mgr;(4)-TCNB groups. Polymer 1, obtained in acetone, revealed a two-dimensional zigzag sheet network between copper(I) ions, whereas 2, synthesized in methylethyl ketone, displayed a three-dimensional porous framework with different functional groups (or atom) in different cavities. The redox, magnetic, and conductive behaviors of both complexes are discussed. It is demonstrated that the two complexes give different physicochemical properties.
本文描述了两种具有相同阴离子和阳离子但拓扑结构和性质截然不同的铜（I）超分子。[Cu(CH(3)CN)(4)]PF(6)与1,2,4,5 - 四氰基苯（TCNB）反应生成两种新型聚合物配位化合物，Cu(2)(TCNB)(3)(2)(Me(2)CO)(4)( )()(1)和Cu(2)(TCNB)(3)(2) (2)，具体取决于所使用的溶剂。晶体结构已通过单晶X射线衍射确定。晶体数据如下。1：C(21)H(15)N(6)O(2)CuPF(6)，单斜晶系，P2(1)/a，a = 11.553(4) Å，b = 16.135(7) Å，c = 15.046(3) Å，β = 108.08(2)度，Z = 4。2：C(15)H(3)N(6)CuPF(6)，正交晶系，Cmcm，a = 28.282(3) Å，b = 10.337(3) Å，c = 16.285(4) Å，Z = 16。在这两种聚合物中，铜（I）离子具有相似的伪四面体环境，四个配位点完全被四个桥连配体占据，即两个μ(2)-TCNB和两个μ(4)-TCNB基团。在丙酮中得到的聚合物1显示出铜（I）离子之间的二维之字形片状网络，而在甲乙酮中合成的2则呈现出三维多孔框架，不同的空腔中有不同的官能团（或原子）。讨论了两种配合物的氧化还原、磁性和导电行为。结果表明这两种配合物具有不同的物理化学性质。
