【摘要】 合成了一组钌多吡啶化合物[Ru（bpy）)2（DMBbimH_x）]^y+（bpy=2,2′-联吡啶,DMBbimH2=7,7′-二甲基-2,2′-苯并联咪唑,1-A:x=2;y=2;1-B:x=1,y=1;1-C:x=0,y=0）并测试了它们的核磁氢谱、紫外吸收和电化学性质。随着DMBbimHx配体逐个脱去质子,配合物的光谱和电化学性质发生明显的变化。有趣的是,脱去一个质子的配合物1-B在不同极性的二氯甲烷和乙腈中的电化学性质呈现明显的差异:在二氯甲烷中,单核的1-B却能发生两步氧化,这是因为在弱极性的溶剂中,[Ru（bpy）₂（DMBbimH）]+阳离子通过氢键结合形成二聚体,[Ru（bpy）₂（DMBbimH）]+阳离子间存在质子耦合电子传递现象。在1-B的二氯甲烷溶液中得到了化合物[Ru（bpy）₂（DMBbimH）]PF₆·2CH2Cl₂（2）的单晶。晶体结构分析表明[Ru（bpy）₂（DMBbimH）]+阳离子确实通过氢键结合形成二聚体,这与电化学测试的结果一致。而在极性较大的乙腈中,氢键二聚体不能稳定存在,在循环伏安曲线上只有一个峰存在。更多还原

【Abstract】 A family of ruthenium（Ⅱ） polypyridyl complexes, namely [Ru（bpy）₂（DMBbimHx）]y+（bpy=2,2′-bipyridine,DMBbimH₂=7,7′-dimethyl-2,2′-bibenzimidazole,1-A: x=2, y=2;1-B: x=1, y=1;1-C: x=0, y=0）, were synthesized and determined by1 H NMR, UV-Vis absorption and electrochemical measurements. With the deprotonation of N-H in DMBbimHx ligands, the spectroscopic and electrochemical properties of complexes showed evident differences.Interestingly, the electrochemical properties of mono-deprotonated1-Bbehaved very differently in dichloromethane and acetonitrile, which is due to different polarities of the solvents. In dichloromethane, mononuclear complex1-B underwent a two-step oxidation. This is because [Ru（bpy）₂（DMBbimH）]+cations are bonded by hydrogen bonds to form dimers in weakly polar solvent, and proton-coupled electron transfer（PCET） exists between the [Ru（bpy）₂（DMBbimH）]+cations. Single crystals of [Ru（bpy）₂（DMBbimH）]PF₆·2 CH₂ Cl₂（2） were obtained from the solution of complex1-Bin dichloromethane. Crystal structure analysis shows that [Ru（bpy）2（DMBbimH）]+cations are bonded by hydrogen bonds to form dimers, which is consistent with the result of the electrochemical measurements. However,hydrogen-bonded dimers couldn′t exist stably in the more polar acetonitrile, therefore only one peak existing in the CV curve. CCDC: 2005043,2.更多还原