Effect of Broken Conjugation on the Excited State: Ether Linkage in the Cyano-Substituted Poly(p-phenylene vinylene) Conjugated Polymer Poly(2,5,2',5'-tetrahexyloxy-8, 7'-dicyano-di-p-phenylene vinylene)

Chasteen, S. V.; Carter, S. A.; Rumbles, Garry

doi:10.1063/1.2196036

Title: Effect of Broken Conjugation on the Excited State: Ether Linkage in the Cyano-Substituted Poly(p-phenylene vinylene) Conjugated Polymer Poly(2,5,2',5'-tetrahexyloxy-8, 7'-dicyano-di-p-phenylene vinylene)

Journal Article · Sun Jan 01 00:00:00 EST 2006 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2196036· OSTI ID:2323468

Chasteen, S. V.; Carter, S. A.;

We investigate the effect of broken conjugation on the excited state dynamics of excimers in cyano-substituted phenylene-vinylene polymers. We compare previous studies on the well-characterized poly(?2,5,2',5'-tetrahexyloxy-8,7'-dicyano-di--phenylene vinylene) (CN-PPV) with poly[oxa-1,4-phenylene-1,2-(1-cyano)-ethenylene-2,5-dioctyloxy-1,4-phenylene-1,2-(2-cyano)-ethenylene-1,4-phenylene] (CN-ether-PPV), in which the conjugation is disrupted by the insertion of an oxygen atom within the polymer backbone. Despite the broken conjugation, the spectroscopic behavior of the two materials is similar, indicating that the cyano group dominates the photophysics in these materials. The emission in CN-ether-PPV is due to a single-chain exciton in solution and due to an interchain excimer in thin film, as previously reported for CN-PPV; however, the excimer absorption and emission in thin film are blueshifted by ~0.2 eV relative to CN-PPV, implying that the excimer in CN-ether-PPV is less stable. Furthermore, substitution of an ether group along the chain results in decay times in both solution and film that are twice as long than in CN-PPV due to the broken conjugation which restricts the exciton within a conjugation segment and reduces its access to internal quenching sites. These properties result in a decay time of 14 ns for CN-ether-PPV film, one of the longest decay times observed in a conjugated polymer film. The long lifetime indicates a large exciton diffusion length, making these species particularly vulnerable to quenching by other materials. This work has implications for the design of conjugated polymers for efficient optoelectronic devices, such as photovoltaics.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 2323468

Report Number(s):: NREL/JA-270-40722; MainId:63043; UUID:58c0501c-dcd4-e411-b769-d89d67132a6d; MainAdminId:45117

Journal Information:: Journal of Chemical Physics, Vol. 124, Issue 21

Country of Publication:: United States

Language:: English

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Title: Effect of Broken Conjugation on the Excited State: Ether Linkage in the Cyano-Substituted Poly(p-phenylene vinylene) Conjugated Polymer Poly(2,5,2',5'-tetrahexyloxy-8, 7'-dicyano-di-p-phenylene vinylene)

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