一种PS给体模型化合物的合成和性能

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (9): 1666.

一种PS给体模型化合物的合成和性能

施锋, 李宏洋, 彭孝军, 陈小强, 张蓉, 王东平, 樊江莉, 孙立成

大连理工大学精细化工国家重点实验室, 大连116012

收稿日期:2003-07-07 出版日期:2004-09-24 发布日期:2004-09-24
基金资助:
国家自然科学基金(批准号:20376010,20128005);国家重点基础研究专项基金资助

Synthesis and Properties of a New Donor Model Compound for PSⅡ

SHI Feng, LI Hong-Yang, PENG Xiao-Jun, CHEN Xiao-Qiang, ZHANG Rong, WANG Dong-Ping, FAN Jiang-Li, SUN Li-Cheng

State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116012, China

Received:2003-07-07 Online:2004-09-24 Published:2004-09-24

摘要/Abstract

摘要： 为了模拟植物光系统的给体部分,设计、合成了配合物2.在该模型化合物中,配体的邻位被2个{[2-羟基-3-(吗啉基-4-甲基)-5-叔丁基-苄基](吡啶-2-甲基)胺基-甲基}取代的苯酚通过酰胺键与光敏体[Ru(bpy)₃]²⁺共价相连.利用ESI-MS和1D,2DNMR(gCOSY,HSQC和HMBC)对化合物结构进行了鉴定,并通过UV-Vis、荧光发射光谱、闪光光解及电化学对其光化学性能和氧化还原特性进行了研究.结果表明,化合物的吸收波长发生红移;激发态寿命长;可螯合双核高价Mn()原子;且Ru3+/Ru2+的氧化电位比Phenol+/Phenol和Mn(,)/Mn()的高,满足自然界PS电子转移的基本要求,可用于PS给体部分的初步研究.

关键词: 配体设计, 含酚配体, 双核配合物, 水氧化, 光系统, 人工光合作用

Abstract: As a model compound for redox components on the donor side of photosystem Ⅱ(PSⅡ) in green plants, a supramolecular complex 2 was synthesized and characterized. In this complex, two {[(2-hydroxy-3-(morpholin-4-ylmethyl)-5-tert-butyl-benzyl)(pyridyl-2-methyl)amino]methyl} arms are linked to the ortho-positions of a phenol which is expected covalently to be linked to Ru(Ⅱ) tris-bipyridine through an amide bond. The arms on the substituted-phenol can coordinate two Mn(Ⅲ) ions. The structure of complex 2 was confirmed by electrospray ionization mass spectrometry(ESI-MS) and 2D-NMR(gCOSY, HSQC and HMBC). Its photochemical and electrochemical properties were studied. The results showed that the MLCT band of the compound was red-shifted compared to that of [Ru(bpy)₃]²⁺ and the luminescence quantum yield was enhanced. In addition, the oxidation potential of ruthenium was higher than the phenol+/phenol and Mn(Ⅲ, Ⅳ)/Mn(Ⅲ), which was consisted with the electron transfer sequence of the donor side of PSⅡ in nature. All these showed that this compound was a good model to mimic the donor side of PSⅡ.

Key words: Ligand design, Phenolate ligand, Dinuclear complex, Water oxidation, Photosystem Ⅱ, Artificial photosynthesis

中图分类号:

O641.4

TrendMD:

施锋, 李宏洋, 彭孝军, 陈小强, 张蓉, 王东平, 樊江莉, 孙立成. 一种PS给体模型化合物的合成和性能. 高等学校化学学报, 2004, 25(9): 1666.

SHI Feng, LI Hong-Yang, PENG Xiao-Jun, CHEN Xiao-Qiang, ZHANG Rong, WANG Dong-Ping, FAN Jiang-Li, SUN Li-Cheng . Synthesis and Properties of a New Donor Model Compound for PSⅡ. Chem. J. Chinese Universities, 2004, 25(9): 1666.

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