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

化学学报 ›› 2004, Vol. 62 ›› Issue (9): 916-922. 上一篇下一篇

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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

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

投稿日期:2003-08-11 修回日期:2004-01-10 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

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 Published:2014-02-17

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摘要/Abstract

为了对绿色植物光系统Ⅱ给体部分进行模拟,合成了1个新的高价双核配合物[Mn₂(Ⅲ,Ⅲ)L(μ-OAc)₂]*PF₆(2a),其中H3L为2,6-二{[(2-羟基-5-叔丁基苄基)(吡啶-2-亚甲基)胺基]亚甲基}-4-甲基苯酚.与目前的PSⅡ模型化合物[Mn₂(Ⅱ,Ⅱ)-(bpmp)(μ-OAc)₂]*ClO₄ (1) [Hbpmp: 2,6-二{[N,N-二(吡啶-2-亚甲基)胺基]亚甲基}-4-甲基苯酚]相比,配合物2a中增加了2个酚羟基及2个叔丁基,由此带来的改进使新模型更接近于自然界四核锰簇(OEC)的真实结构.在此基础上,我们将该配体通过酰胺键与[Ru(bPy)₃]²⁺相连设计了光诱导电子转移模型化合物2b.其中[Ru(bPy)₃]²⁺具有良好的光电性能,用于模拟PSⅡ中酶P₆₈₀.通过紫外可见、红外、荧光发射光谱及电化学对化合物进行了光、电性能研究,结果表明配合物2b具有良好的光物理性质,而且2b中Ru³⁺/Ru²⁺的氧化还原电位比Phenol⁺/Phenol和Mn(Ⅲ,Ⅳ)/Mn(Ⅲ,Ⅲ)的高,说明2b配位金属Mn后可满足自然界PSⅡ电子转移的基本要求,是用来模拟PSⅡ给体部分较理想的模型.

关键词: 双核锰, 三联吡啶钌, 人工光合作用, 光系统Ⅱ, 含酚配体

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 E_1/2 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

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李宏洋, 施锋, 彭孝军, 张蓉, 陈小强, 张丽珠, 孙立成. 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[J]. 化学学报, 2004, 62(9): 916-922.

LI Hong-Yang, SHI Feng, PENG Xiao-Jun, ZHANG Rong, CHEN Xiao-Qiang, ZHANG Li-Zhu, SUN Li-Cheng. 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[J]. Acta Chimica Sinica, 2004, 62(9): 916-922.

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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

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

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