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Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers

Rolf Andernach, Hendrik Utzat, Stoichko Dimitrov Orcid Logo, Iain McCulloch, Martin Heeney, James R. Durrant, Hugo Bronstein

Journal of the American Chemical Society, Volume: 137, Issue: 32, Pages: 10383 - 10390

Swansea University Author: Stoichko Dimitrov Orcid Logo

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DOI (Published version): 10.1021/jacs.5b06223

Abstract

We report the synthesis of a novel polythiophene-based host–guest copolymer incorporating a Pt–porphyrin complex (TTP–Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorptio...

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Published in: Journal of the American Chemical Society
ISSN: 0002-7863 1520-5126
Published: 2015
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URI: https://cronfa.swan.ac.uk/Record/cronfa31797
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spelling 2017-02-23T16:39:45.2037268 v2 31797 2017-01-27 Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers 9fc26ec1b8655cd0d66f7196a924fe14 0000-0002-1564-7080 Stoichko Dimitrov Stoichko Dimitrov true false 2017-01-27 EEN We report the synthesis of a novel polythiophene-based host–guest copolymer incorporating a Pt–porphyrin complex (TTP–Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple time scales and investigated the mechanism of triplet exciton formation. During sensitization, singlet exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt–porphyrin to the polymer and found that 60% of the complex triplet excitons were transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet–triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and upconversion layers. Journal Article Journal of the American Chemical Society 137 32 10383 10390 0002-7863 1520-5126 22 7 2015 2015-07-22 10.1021/jacs.5b06223 http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&amp;SrcAuth=ORCID&amp;SrcApp=OrcidOrg&amp;DestLinkType=FullRecord&amp;DestApp=WOS_CPL&amp;KeyUT=WOS:000359962000061&amp;KeyUID=WOS:000359962000061 COLLEGE NANME Engineering COLLEGE CODE EEN Swansea University 2017-02-23T16:39:45.2037268 2017-01-27T13:46:00.9255782 Faculty of Science and Engineering School of Engineering and Applied Sciences - Uncategorised Rolf Andernach 1 Hendrik Utzat 2 Stoichko Dimitrov 0000-0002-1564-7080 3 Iain McCulloch 4 Martin Heeney 5 James R. Durrant 6 Hugo Bronstein 7
title Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
spellingShingle Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
Stoichko Dimitrov
title_short Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
title_full Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
title_fullStr Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
title_full_unstemmed Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
title_sort Synthesis and Exciton Dynamics of Triplet Sensitized Conjugated Polymers
author_id_str_mv 9fc26ec1b8655cd0d66f7196a924fe14
author_id_fullname_str_mv 9fc26ec1b8655cd0d66f7196a924fe14_***_Stoichko Dimitrov
author Stoichko Dimitrov
author2 Rolf Andernach
Hendrik Utzat
Stoichko Dimitrov
Iain McCulloch
Martin Heeney
James R. Durrant
Hugo Bronstein
format Journal article
container_title Journal of the American Chemical Society
container_volume 137
container_issue 32
container_start_page 10383
publishDate 2015
institution Swansea University
issn 0002-7863
1520-5126
doi_str_mv 10.1021/jacs.5b06223
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Uncategorised{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Uncategorised
url http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&amp;SrcAuth=ORCID&amp;SrcApp=OrcidOrg&amp;DestLinkType=FullRecord&amp;DestApp=WOS_CPL&amp;KeyUT=WOS:000359962000061&amp;KeyUID=WOS:000359962000061
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description We report the synthesis of a novel polythiophene-based host–guest copolymer incorporating a Pt–porphyrin complex (TTP–Pt) into the backbone for efficient singlet to triplet polymer exciton sensitization. We elucidated the exciton dynamics in thin films of the material by means of Transient Absorption Spectrosopcy (TAS) on multiple time scales and investigated the mechanism of triplet exciton formation. During sensitization, singlet exciton diffusion is followed by exciton transfer from the polymer backbone to the complex where it undergoes intersystem crossing to the triplet state of the complex. We directly monitored the triplet exciton back transfer from the Pt–porphyrin to the polymer and found that 60% of the complex triplet excitons were transferred with a time constant of 1087 ps. We propose an equilibrium between polymer and porphyrin triplet states as a result of the low triplet diffusion length in the polymer backbone and hence an increased local triplet population resulting in increased triplet–triplet annihilation. This novel system has significant implications for the design of novel materials for triplet sensitized solar cells and upconversion layers.
published_date 2015-07-22T03:38:52Z
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score 11.012678