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

我们新合成了各种镍（I 1）和铜（II）离子的单核和双核混合配体配合物，并对我们研究过的已知的单核配合物进行了重新研究，确定了它们的晶体结构。对于单核配合物，它们的通式是：M (dike) (diam) X, M (dike) (triam) X, M (dike) (tetam) X，其中M=Ni （i 1）或Cu (i 1), dike= -二酮酸酯，diam=乙二胺衍生物，triam=二乙三胺，tetam=三乙四胺，它们都是n -烷基化的，X=B (Ph)_4^-, CIO_4^-, NO_3^-，卤化物或伪卤化物阴离子。对于双核配合物，其通式为M_2 (teke) (polyam)_2X_2，其中teke表示支化的四乙酸酯配体作为桥接基团，如1,1,2,2 -四乙酸乙酯配体和polyam= n -烷基化的diam、triam或tetam。其他类型的双核配合物有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配体作为桥接配体。形成稳定的混合配体配合物的重要因素是配体的合适组合，即，在这种情况下，我们使用大体积的多胺和较少空间阻碍的二酮酸盐或四酮酸盐。立体化学调节是由大体积多胺的空间效应、聚酮酸的电子效应和阴离子的配位能力决定的。除了这些结果外，幸运的是，这些混合配体配合物在各种有机溶剂中都很容易溶解，并在溶液中表现出典型的溶剂变色和热变色等显色性。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.