Hamblin Jacqueline, Tuna Floriana, Bunce Siona, Childs Laura J, Jackson Alexander, Errington William, Alcock Nathaniel W, Nierengarten Helene, Van Dorsselaer Alain, Leize-Wagner Emmanuelle, Hannon Michael J
Department of Chemistry, University of Leicester, Leicester, UK.
Chemistry. 2007;13(33):9286-96. doi: 10.1002/chem.200700848.
The effect of changes in the angles at the connection points of linear/circular helicates is explored as a route to control the nuclearity and architecture of metallo-supramolecular arrays. This effect is probed by changing the geometry of the metal centre used to assemble bis-pyridylimine ligands that contain a 1,3-bis(aminomethyl) benzene spacer group. Tetrahedral metal ions favour linear dimers, whereas octahedral nickel(II) predominantly gives a triangular circular helicate. Five-coordinate copper(II) falls in the middle of these extremes and results in the formation of solvent-dependent mixtures of dimer and trimer. The trinuclear, triangular, circular helicate structures, which result from coordination to copper(II) and nickel(II), are structurally characterised by X-ray crystallography and reveal that the units can aggregate into hexagonal arrays that contain anion-filled tube-like channels in the solid state.
探索线性/环状螺旋配合物连接点处角度变化的影响，以此作为控制金属超分子阵列的核数和结构的途径。通过改变用于组装含有1,3-双（氨甲基）苯间隔基团的双吡啶亚胺配体的金属中心的几何形状来探究这种影响。四面体金属离子有利于形成线性二聚体，而八面体镍（II）主要生成三角形环状螺旋配合物。五配位铜（II）处于这两种极端情况之间，导致形成二聚体和三聚体的溶剂依赖性混合物。通过与铜（II）和镍（II）配位形成的三核、三角形、环状螺旋配合物结构，经X射线晶体学表征，结果表明这些单元在固态下可聚集成含有阴离子填充管状通道的六边形阵列。
