含席夫碱桥联配体的双核金属钌配合物的合成及其性能研究(英文)

Synthesis and Properties of Dinuclear Ruthenium Complexes with Schiff Base Bridging Ligands

合成了3种双核钌配合物[Ru（bpy）2]2{[（PyCHN）-Ph-0-C6H4-12R}（C104）4，bpy=2，2＇-联吡啶，PyCHN=N-2．吡啶亚甲基，R=无（1），-C（CH3）2（2），-SO2（3）并进行了有关表征。电化学研究表明：配合物3的△E和憨值最大，说明苯环和硫原子之间存在着较强的（P（π）-d）丌相互作用，有助于获得较强的金属-金属相互作用。配合物1，2，3都有混合价，通过Hush方程可以得到V女的值大概为320-420cm^-1。这些结果表明：Schiff碱作为桥配体对于调配金属-金属相互作用并将其作为分子导线起着特殊的作用。

Binuclear ruthenium complexes [Ru （bpy）2]2 {[（PyCHN）-Ph-O-C6H4-]2R} （CIO4）4. where bpy =2,2＇- bipyridine, PyCHN=N-2-pyridylmethylene, R=none for 1, -C（CH3）2 for 2 and -SO2 for 3, have been prepared and characterized. Electrochemical studies reveal that the AE and Ko for complexes 1, 2 and 3 are surprisingly and unprecedentedly large. However, the complex 3 gives larger AE and Kc. It is suggested that the strong （p（π）-d）π interactions between the phenyl rings and the sulfur atom should be helpful to achieve stronger metal-metal interaction. For mixed-valence species of complexes 1, 2 and 3, Vab can be obtained by Hush equation with a value of 320-420 cm-1. These results indicate that the Schiff base bridging ligands show particular efficiency for mediating the metal-metal interactions and for using as molecular wires.