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Properties of the Intramolecular Excited Charge-Transfer States of Donor-Acceptor Phenothiazine Derivatives
Liu Tao,Yuan Yanqiu,Wei Yonggang,Guo Qingxiang*
Author NameAffiliationE-mail
Liu Tao Department of Chemistry, University of Science and Technology of China, Hefei 230026  
Yuan Yanqiu Department of Chemistry, University of Science and Technology of China, Hefei 230026  
Wei Yonggang Department of Chemistry, University of Science and Technology of China, Hefei 230026  
Guo Qingxiang* Department of Chemistry, University of Science and Technology of China, Hefei 230026 qxguo@ustc.edu.cn 
Abstract:
A series of N-bonded donor-acceptor derivatives of phenothiazine containing benzene (PHPZ), anisole (ANPZ), pyridine (PYPZ), naphthalene (NAPZ), acetophenone (PEPZ), and benzonitrile (BNPZ) as an electron acceptor was synthesized. Their photophysical properties were investigated in solvents of different polarities by absorption and emission techniques. These studies clearly reveals the existence of an intramolecular charge transfer (ICT) excited state in the latter four compounds. The solvent dependent Stokes shift values were analyzed by the modified Lippert-Mataga equation to obtain the excited state dipole moment values. The large excited state dipole moment suggests that the full electron transfer takes place in the A-D systems. The obtained values of redox potentials indicate that both subunits of all the A-D molecules studied interact very weakly in the ground states. The results obtained from the analysis of the CT fluorescence spectra confirm that the small conformational changes accompanying excited state charge transfer, the twist angle between the donor and acceptor moieties in the excited 1CT state seems to be similar to that in the ground state.
Key words:  Phenothiazine, Intramolecular charge transfer, Donor-acceptor, dipole moment
FundProject:
吩噻嗪衍生物的分子内电荷转移激发态的特性
刘涛,袁燕秋,魏用刚,郭庆祥*
摘要:
合成了一系列的N-10位取代的吩噻嗪给体受体化合物,这些受体包括苯、苯甲醚、吡啶、萘、苯乙酮和苯乙腈.研究了不同极性溶剂中这些化合物的分子内的光诱导电荷转移现象.稳态荧光的溶剂化效应和较大的Stokes位移清楚表明,仅仅后四种吩噻嗪衍生物的激发态存在着分子内的电荷转移,而苯和苯甲醚取代吩噻嗪因为受体部分氧化电势低,所以不具有这种特性.修正过的Lippert-Mataga公式被用来分析Stokes位移值,从而获得激发态偶极矩.较大的激发态偶极矩说明在激发态时这四种给体受体化合物体系内发生了完全的电子转移.氧化还原电势的数据表明基态时这四种衍生物给体受体部分的作用比较弱.分析荧光光谱获得的结果说明伴随着电荷转移这四种衍生物的激发态构型变化比较小,给体和受体间的扭转角在电荷转移后的激发态与在基态时相似.
关键词:  吩噻嗪  分子内电荷转移  给体-受体  偶极矩
DOI:10.1088/1674-0068/18/5/798-806
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