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利用 Ni II- I- Ni II联接单元合成并表征了四氮大环镍 (II)配合物二聚体 [(Ni L) 2 I](I3) 3,这里 L=5 ,7,7,1 2 ,1 4,1 4-六甲基 - 1 ,4,8,1 1 -四氮杂环十四 - 4 ,1 1 -二烯。 X射线晶体结构及光谱数据显示 [(Ni L) 2 I](I3) 3是三明治结构 ,对称中心为碘离子 ,两个大环配合物平面相互平行 ,整个组装体的对称性为 D4d。结构数据还表明使 Ni II- I- Ni II单元起稳定作用的主要是碘离子与金属离子间的静电作用 ,还有较弱的共价相互作用。在这种二聚体中 ,金属离子不仅作为大环配合物的中心原子 ,而且在 Ni II- I- Ni II单元中还作为碘阴离子的受体。 [(Ni L ) 2 I](I3) 3的变温紫外可见吸收光谱表明其分解温度约为 375 K。因为这种四氮大环金属配合物二聚体含碘离子一价及三价碘阴离子 ,故有可能在将太阳能转变为电能的光电化学电池中作为电解质而获得应用。
The dimeric [(Ni L) 2 I] (I3) 3 was synthesized and characterized by Ni II-I-Ni II coupling unit, where L = 5, 7, 7, 2, 1 4,1 4-hexamethyl-1, 4,8,1 1 -tetraazacyclo 14- 4,1 1-diene. X-ray crystal structure and spectral data show that [(Ni L) 2 I] (I3) 3 is a sandwich structure and the symmetry center is iodide. The plane of the two macrocyclic complexes are parallel to each other, and the symmetry of the whole assembly is D4d. The structural data also shows that the stabilizing effect of Ni II-I-Ni II units is mainly due to the electrostatic interaction between iodide and metal ions and weak covalent interaction. In this dimer, metal ions act not only as central atoms in the macrocyclic complexes but also as acceptors of iodine anions in Ni II-I-Ni II units. The UV-Vis absorption spectra of [(Ni L) 2 I] (I3) 3 showed that its decomposition temperature was about 375 K. Because this tetra-azo macrocyclic metal complex dimer contains iodide ion monovalent and trivalent iodine anions, it is possible to find application as an electrolyte in photoelectrochemical cells that convert solar energy into electrical energy.