期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 18, 期 27, 页码 18536-18548出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c6cp00644b
关键词
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资金
- ANR PICASSO project [ANR 2011-BS08-0009]
- joint DFG/ANR MolNanoMat project [DFG BU1032/3-1, ANR 2011-INTB-1012-01]
- European Community via the Interreg IV-A program [C25]
- Universite de Strasbourg
Conjugated donor-acceptor block co-oligomers that self-organize into D-A mesomorphic arrays have raised increasing interest due to their potential applications in organic solar cells. We report here a combined experimental and computational study of charge transfer (CT) state formation and recombination in isolated donor-spacer-acceptor oligomers based on bisthiophene-fluorene (D) and perylene diimide (A), which have recently shown to self-organize to give a mesomorphic lamellar structure at room temperature. Using femtosecond transient absorption spectroscopy and Time-Dependent Density Functional Theory in combination with the Marcus-Jortner formalism, the observed increase of the CT lifetimes is rationalized in terms of a reduced electronic coupling between D and A brought about by the chemical design of the donor moiety. A marked dependence of the CT lifetime on solvent polarity is observed, underscoring the importance of electrostatic effects and those of the environment at large. The present investigation therefore calls for a more comprehensive design approach including the effects of molecular packing.
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