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基于二甲基苯并联咪唑的钌(Ⅱ)多吡啶配合物的合成、光谱和电化学性质(英文)

Synthesis, Spectroscopic and Electrochemical Properties of Ruthenium(Ⅱ) Polypyridyl Complexes with Dimethyl-bibenzimidazolate Ligands

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【作者】 曹曼丽尚美洁刘文婷尹伟姚苏洋叶保辉

【Author】 CAO Man-Li;SHANG Mei-Jie;LIU Wen-Ting;YIN Wei;YAO Su-Yang;YE Bao-Hui;Department of Chemistry, Guangdong University of Education;Engineering Technology Development Center of Advanced Materials & Energy Saving and Emission Reduction in Guangdong Colleges and Universities;MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-sen University;

【通讯作者】 姚苏洋;叶保辉;

【机构】 广东第二师范学院化学系广东省普通高校先进材料与节能减排工程技术开发中心中山大学化学学院

【摘要】 合成了一组钌多吡啶化合物[Ru(bpy))2(DMBbimHx)]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。

【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.

【基金】 国家自然科学基金(No.21001031);2019年广东省教育厅“材料化学”特色专业立项建设项目;广东第二师范学院教学质量与教学改革工程项目(No.2018zygxk04,2019syzy03);广东第二师范学院材料化学应用型人才培养课程建设项目(8)资助
  • 【文献出处】 无机化学学报 ,Chinese Journal of Inorganic Chemistry , 编辑部邮箱 ,2020年09期
  • 【分类号】O641.4
  • 【下载频次】109
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