Neuteboom Edda E, van Hal Paul A, Janssen René A J
Molecular Materials and Nanosystems, Eindhoven University of Technology, P.O. Box 513 5600 MB Eindhoven, The Netherlands.
Chemistry. 2004 Aug 20;10(16):3907-18. doi: 10.1002/chem.200400097.
Two new donor-acceptor copolymers that consist of an enantiomerically pure oligo(p-phenylene vinylene) main chain with dangling perylene bisimides have been synthesized by using a Suzuki cross-coupling polymerization. Absorption and circular dichroism spectroscopy revealed that the transition dipole moments of the donor in the main chain and the dangling acceptor moieties of the copolymers are coupled and in a helical orientation in solution, even at elevated temperatures. A strong fluorescence quenching of both chromophores indicates an efficient photoinduced charge transfer after photoexcitation of either donor or acceptor. The formation and recombination kinetics of the charge-separated state were investigated in detail with femtosecond and near-steady-state photoinduced absorption spectroscopy. The charge-separated state forms within 1 ps after excitation, and recombination occurs with a time constant of 45-60 ps, both in solution and in the solid state. These optical characteristics indicate a short distance and appreciable interaction between the electron-rich donor chain and the dangling electron-poor acceptor chromophores.
通过铃木交叉偶联聚合反应合成了两种新型供体-受体共聚物,它们由具有悬挂苝二酰亚胺的对映体纯的聚对苯撑乙烯主链组成。吸收光谱和圆二色光谱表明,即使在高温下,共聚物主链中的供体和悬挂的受体部分的跃迁偶极矩在溶液中也是耦合的,并且呈螺旋取向。两种发色团的强烈荧光猝灭表明,在供体或受体光激发后发生了有效的光诱导电荷转移。利用飞秒和近稳态光诱导吸收光谱详细研究了电荷分离态的形成和复合动力学。在溶液和固态中,电荷分离态在激发后1 ps内形成,复合发生的时间常数为45 - 60 ps。这些光学特性表明富电子供体链与悬挂的贫电子受体发色团之间距离短且相互作用显著。