The 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)

S. V. Chasteen, S. A. Carter, Gary Rumbles

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

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- p -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.

Original languageEnglish
Article number214704
JournalJournal of Chemical Physics
Volume124
Issue number21
DOIs
Publication statusPublished - Jun 7 2006

Fingerprint

Conjugated polymers
conjugation
Excited states
linkages
Ether
ethers
excimers
polymers
excitation
excitons
Quenching
Polymers
decay
quenching
Thin films
thin films
diffusion length
optoelectronic devices
Polymer films
Optoelectronic devices

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

@article{bb157f73ce8f4c5a813de01076d168c0,
title = "The 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)",
abstract = "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- p -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.",
author = "Chasteen, {S. V.} and Carter, {S. A.} and Gary Rumbles",
year = "2006",
month = "6",
day = "7",
doi = "10.1063/1.2196036",
language = "English",
volume = "124",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "21",

}

TY - JOUR

T1 - The effect of broken conjugation on the excited state

T2 - 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)

AU - Chasteen, S. V.

AU - Carter, S. A.

AU - Rumbles, Gary

PY - 2006/6/7

Y1 - 2006/6/7

N2 - 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- p -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.

AB - 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- p -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.

UR - http://www.scopus.com/inward/record.url?scp=34547853505&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34547853505&partnerID=8YFLogxK

U2 - 10.1063/1.2196036

DO - 10.1063/1.2196036

M3 - Article

VL - 124

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 21

M1 - 214704

ER -