Regulation of the Structure of di-nuclear complexes and chromotropic behaviors of the complexes

我们新合成了各种单核和双核混合配体配合物与镍（I1）和铜（II）离子，也重新研究了著名的单核配合物，我们研究确定其晶体结构。对于单核配合物，它们的通式为：M（dike）（diam）X，M（dike）（triam）X，M（dike）（tetam）X其中M=Ni（i 1）或Cu（i 1），dike= β-二酮基，diam=乙二胺衍生物，triam=二亚乙基三胺，tetam=三亚乙基四胺，它们都是N-烷基化的，X=B（Ph）_4^-，ClO_4 ^-，NO_3^-，卤素或拟卤素阴离子。双核配合物的通式为M_2（teke）（polyam）_2X_2，其中teke是指作为桥连基团的支链四酮配体，如1，1，2，2-四乙酰基乙酸酯配体和polyam= N-烷基化的二胺、三胺或四胺。另一类双核配合物是M_2（CO_3）（dike）_2（diam）_2、M_2（C_2O_4）（dike）_2（diam）_2或M_2（X）_2（dike）_2（diam）_2，其中（CO_3）、（C_2O_4）或（X）_2配体作为桥联配体。例如，在这种情况下，我们使用大体积聚胺和空间位阻较小的二酮化物或四酮化物。大体积多胺的空间效应、聚酮的电子效应以及所用阴离子的配位能力是立体化学调控的主要原因。除了这些结果之外，幸运的是，这些混合配体配合物在各种有机溶剂中非常可溶，并且在溶液中显示出特征的向色性，例如溶剂化变色和热变色。对于双核配合物的晶体，我们可以观察到弱的反铁磁相互作用，这取决于所使用的桥接配体的性质。

We have newly synthesized various kinds of mono- and di-nuclear mixed ligand complexes with nickel (I 1) and copper (II) ions and also have reinvestigated the well-known mononuclear complexes studied by us for determining their crystal structures. For the mononuclear complexes, their general formulas are : M (dike) (diam) X, M (dike) (triam) X, M (dike) (tetam) X where M=Ni (i 1) or Cu (i 1), dike=beta-diketonate, diam=ethylenediamine derivatives, triam=diethylenetriamine, tetam=triethylenetetraamine which are all N-alkylated, and X=B (Ph)_4^-, CIO_4^-, NO_3^-, halide or pseudohalide anions. For the di-nuclear complexes, they are shown M_2 (teke) (polyam)_2X_2 as the general formula i n which teke means the branched tetraketonate ligand worked as the bridging group such as 1, 1, 2, 2-tetraacetylethanate ligandand polyam=N-alkylated diam, triam or tetam used before. Another types of di-nuclear complexes are M_2 (CO_3) (dike)_2 (diam)_2, M_2 (C_2O_4) (dike)_2 (diam)_2, or M_2 (X)_2 (dike)_2 (diam)_2, in which (CO_3), (C_2O_4)or(X)_2 ligand act as the bridging ligands.The important factor to form stable mixed ligand complexes is the suitable combination of the ligands, i. e., in this case we use the bulky polyamine and the less-sterically hindered diketonate or tetraketonate. The stereochemical regulation are resulted from the steric effect of the bulky polyamine, electronic effect of polyketonate and the coordinating ability of the anions used. In addition to these results, fortunately, these mixed ligand complexes are very soluble in various organic solvents and show the characteristic chromotropismes such as solvatochromism and thermochromism in solution. For crystals of di-nuclear complexes, we could observe the weak antiferromagnetic interactions which depends upon the nature of the bridging ligands used.