Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (9): 916-922. Previous Articles     Next Articles

Mn(Ⅲ,Ⅲ)配合物及含酚配体[N4O3]3--Ru(bPy)3模型化合物的性能研究

李宏洋, 施锋, 彭孝军, 张蓉, 陈小强, 张丽珠, 孙立成   

  1. 大连理工大学精细化工国家重点实验室,大连中山路158号40信箱,116012
  • 收稿日期:2003-08-11 修回日期:2004-01-10 出版日期:2004-05-14 发布日期:2014-02-17
  • 通讯作者: 彭孝军,E-mail:pengxj@chem.dlut.edu.cn E-mail:pengxj@chem.dlut.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.20376010,20128005)和国家基础研究重大项目前期研究专项资助.

Properties of a Dinuclear Mn(Ⅲ,Ⅲ) Complex with a Tri-phenolate Ligand [N4O3]3- and a New Complex Containing a Ligand Covalently Linked to Ruthenium Tris-bipyridine

LI Hong-Yang, SHI Feng, PENG Xiao-Jun, ZHANG Rong, CHEN Xiao-Qiang, ZHANG Li-Zhu, SUN Li-Cheng   

  1. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian Zhongshan Road 158, Box 40, 116012
  • Received:2003-08-11 Revised:2004-01-10 Online:2004-05-14 Published:2014-02-17

A new high valent complex [Mn2(Ⅲ,Ⅲ)L(μ-OAc)2]·PF6(2a) was prepared, where L was the trianion of 2,6-bis{[(2-hydroxy-5-tert-butylbenzyl)(pyridyl 2 methyl) amino] methyl} 4 methylphenol, which contains two additional phenolate groups and two tert-butyl groups compared to its parent [Mn2(Ⅱ,Ⅱ)(bpmp)(μ-OAc)2]·ClO4(1).These improvements narrowed the disparity between the new model and (Mn)4 cluster (OEC in nature).Moreover, L was modified to be covalently linked with Ru(Ⅱ) tris-bipyridine through an amide bond to construct a complex 2b for the study of photoinduced electron transfer (PET).UV-vis, IR, emission spectra and electrochemistry were used to investigate their photochemistry properties.The results showed that 2b has good photochemistry properties and the E1/2 of Ru3+/Ru2+ was higher than those of phenol+/phenol and Mn(Ⅲ,Ⅳ)/Mn(Ⅲ,Ⅲ).After coordination of manganese ions, the electron transfer process in the model complex conforms to the basic principles of electron donor side of photosystem Ⅱ (PSⅡ) in nature.

Key words: dinuclear manganese, ruthenium(Ⅱ)tris-bipyridine, artificial photosynthesis, PSⅡ, phenolate ligand