title: Conformation-related exciton localization and charge-pair formation in polythiophenes: ensemble and single-molecule study.
abstract: We study conformation-dependent photophysical properties of polythiophene (PT) by molecular dynamics simulations and by ensemble and single-molecule optical experiments. We use a graft copolymer consisting of a polythiophene backbone and long polystyrene branches and compare its properties with those obtained on the same polythiophene derivative without the side chains. Coarse-grain molecular dynamics simulations show that in a poor solvent, the PT without the side chains (PT-R) forms a globulelike conformation in which distances between any two conjugated segments on the chain are within the Forster radius for efficient energy transfer. In the PT with the polystyrene branches (PT-PS), the polymer main PT chain retains an extended coillike conformation, even in a poor solvent, and the calculated distances between conjugated segments favor energy transfer only between a few neighboring chromophores. The theoretical predictions are confirmed by measurements of fluorescence anisotropy and fluorescence blinking of the polymers' single chains. High anisotropy ratios and two-state blinking in PT-R are due to localization of the exciton on a single conjugated segment. These signatures of exciton localization are absent in single chains of PT-PS. Electric-field-induced quenching measured as a function of concentration of PT dispersed in an inert matrix showed that in well-isolated chains of PT-PS, the exciton dissociation is an intrachain process and that aggregation of the PT-R chains causes an increase in quenching due to the onset of interchain interactions. Measurements of the field-induced quenching on single chains indicate that in PT-R, the exciton dissociation is a slower process that takes place only after the exciton is localized on one conjugated segment.
authors.affiliation: Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Ookayama 2-12-1-S8, Meguro-ku, Tokyo 152-8552, Japan.
authors.forename: Toshikazu
authors.initials: T
authors.lastname: Sugimoto
authors.forename: Satoshi
authors.initials: S
authors.lastname: Habuchi
authors.forename: Kenji
authors.initials: K
authors.lastname: Ogino
authors.forename: Martin
authors.initials: M
authors.lastname: Vacha
mesh_terms: D003198:Computer Simulation; D008968:Molecular Conformation; D015394:Molecular Structure; D011108:Polymers / Q000737:chemistry*; D011137:Polystyrenes / Q000737:chemistry; D013876:Thiophenes / Q000737:chemistry*
chemical_list: D011108:Polymers; D011137:Polystyrenes; D013876:Thiophenes; C066730:polythiophene