脲基嘧啶酮四氢键二茂铁二聚体:电子相互作用的调控(英文)  

Ureidopyrimidinone Quadruple Hydrogen-Bonded Ferrocene Dimer: Control of Electronic Communication

作　　者：王素敏[1] 赵绒娜 王奇观[1] 郭浩[1] 李金华[1] 张文慧[1] 

机构地区：[1]西安工业大学材料与化工学院,陕西省光电功能材料与器件重点实验室,西安710032

出　　处：《物理化学学报》2016年第3期611-616,共6页Acta Physico-Chimica Sinica

基　　金：supported by the National Natural Science Foundation of China(21103133);Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education;Natural Science Foundation of Shaanxi Province,China(2015JM5224);Shaanxi Provincial Education Department Program,China(2013JK0678);National Training Programs of Innovation and Entrepreneurship for Undergraduates,China(201510702030)

摘　　要：以脲基嘧啶酮四重氢键为桥联单元,组装了二茂铁同体二聚体(1?1)。电化学实验显示1?1中两个等同的二茂铁基团的氧化还原电位差值(ΔE)达260 mV,说明1?1中两个二茂铁基团间通过四氢键发生了显著的电子相互作用。在1?1/CHCl_3中逐步加入0.5、1和2等摩尔的CF_3COOH时,由于脲基嘧啶酮四氢键的逐步解离,二茂铁间的电子相互作用强度逐渐减弱,其ΔE从260 mV逐步减小至150、100和0 mV,此时再加入三乙胺又可以使电子相互作用逐步恢复至初始状态,说明通过加入质子酸、碱可有效调控四氢键体系中发色团间通过氢键的电子相互作用。A ferrocene homodimer was assembled via the ureidopyrimidinone quadruple hydrogen-bonded module in this paper. Remarkable electronic communication was found between the two ferrocene centers across the ureidopyrimidinone bridge in chloroform. The separation between the two redox potentials（ΔE） of the ferrocenyl moieties was 260 mV. Upon protonation of the hydrogen-bonded bridge by successive addition of 0.5, 1, and 2 equivalents of trifluoroacetic acid, the extent of the electronic communication between the subunits gradually lowered, with ΔE decreasing to 150, 100, and 0 mV, respectively, because of the stepwise dissociation of the pyrimidinone hydrogen-bonded bridge. This phenomenon is reversible, and the initial voltammogram can be recovered stepwise by successive addition of triethylamine, demonstrating effective control of the electronic communication between two ferrocene centers.

关 键 词：脲基嘧啶酮 四氢键 电子相互作用 调控 二茂铁 

分 类 号：O641.3[理学—物理化学] O627.81[理学—化学]