title: H- and J-aggregate behavior in polymeric semiconductors.
abstract: Aggregates of conjugated polymers exhibit two classes of fundamental electronic interactions: those occurring within a given chain and those occurring between chains. The impact of such excitonic interactions on the photophysics of polymer films can be understood using concepts of J- and H-aggregation originally developed by Kasha and coworkers to treat aggregates of small molecules. In polymer assemblies, intrachain through-bond interactions lead to J-aggregate behavior, whereas interchain Coulombic interactions lead to H-aggregate behavior. The photophysics of common emissive conjugated polymer films are determined by a competition between intrachain, J-favoring interactions and interchain, H-favoring interactions. We review formalisms describing absorption and photoluminescence lineshapes, based on intra- and intermolecular excitonic coupling, electron-vibrational coupling, and correlated energetic disorder. Examples include regioregular polythiophenes, pheneylene-vinylenes, and polydiacetylene.
authors.affiliation: Department of Chemistry, Temple University, Philadelphia, Pennsylvania 19122; email: spano@temple.edu.
authors.forename: Frank C
authors.initials: FC
authors.lastname: Spano
authors.forename: Carlos
authors.initials: C
authors.lastname: Silva
mesh_terms: D008956:Models, Chemical; D008958:Models, Molecular; D000078789:Polyacetylene Polymer; D011108:Polymers / Q000737:chemistry*; D053279:Polyynes / Q000737:chemistry*; D012666:Semiconductors; D013876:Thiophenes / Q000737:chemistry*; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000078789:Polyacetylene Polymer; D011108:Polymers; D013876:Thiophenes; D014753:Vinyl Compounds; C520682:poly(2-methoxy-5-(2'-ethylhexyloxy)-p-phenylenevinylene); C507295:poly(3-hexylthiophene); D053279:Polyynes; C082361:polydiacetylene