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π-Stacking in Conjugated Polymers and Oligomers: A Structural and Spectroscopic Study

Published online by Cambridge University Press:  10 February 2011

M. David Curtis
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Wendy Blanda
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Jeffrey K. Politis
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Anthony H. Francis
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Jihoon Lee
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Jeff W. Kampf
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
Lebzylisbeth Gonzalez-Ronda
Affiliation:
Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109-2022
David C. Martin
Affiliation:
Department of Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
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Abstract

Regioregular, alkyl-substituted poly(heteroaromatics) tend to crystallize in π-stacked structures as opposed to the herringbone pattern characteristic of non-substituted, planar aromatic molecules, e.g. sexithiophene. π-Stacking, favored by the crystallization of the sidechains, induces planarity in the conjugated backbone. The increased planarity causes a large (50-100 nm) shift in λmax (abs.) compared to the solution phase in which the backbone is twisted out of coplanarity, π-Stacking is a form of ground state aggregation that causes “fine structure” on the absorption peak. Excitation into the aggregate states rapidly leads to the formation of excimers as shown by the excitation spectra. In -stacked polymers, photoluminescence is almost entirely from the excimer states.

Type
Research Article
Copyright
Copyright © Materials Research Society 1999

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