Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.

The energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient a...

Deskribapen osoa

Xehetasun bibliografikoak
Egile Nagusiak: Beljonne, D, Pourtois, G, Silva, C, Hennebicq, E, Herz, L, Friend, R, Scholes, G, Setayesh, S, Mullen, K, Bredas, J
Formatua: Journal article
Hizkuntza:English
Argitaratua: 2002
_version_ 1826274215503855616
author Beljonne, D
Pourtois, G
Silva, C
Hennebicq, E
Herz, L
Friend, R
Scholes, G
Setayesh, S
Mullen, K
Bredas, J
author_facet Beljonne, D
Pourtois, G
Silva, C
Hennebicq, E
Herz, L
Friend, R
Scholes, G
Setayesh, S
Mullen, K
Bredas, J
author_sort Beljonne, D
collection OXFORD
description The energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient absorption spectra measured in solution and in films allows disentangling of the contributions arising from intrachain and from interchain energy-migration phenomena. Intrachain processes dominate in solution where photoexcitation of the polyindenofluorene units induces a rather slow energy transfer to the perylene end moieties. In films, close contacts between chains favors interchain transport of the excited singlet species (from the conjugated bridge of one chain to the perylene unit of a neighboring one); this process is characterized by a 1-order-of-magnitude increase in transfer rate with respect to solution. This description is supported fully by the results of quantum-chemical calculations that go beyond the usual point-dipole model approximation and account for geometric relaxation phenomena in the excited state before energy migration. The calculations indicate a two-step mechanism for intrachain energy transfer with hopping along the conjugated chains as the rate-limiting step; the higher efficiency of the interchain transfer process is mainly due to larger electronic coupling matrix elements between closely lying chains.
first_indexed 2024-03-06T22:40:04Z
format Journal article
id oxford-uuid:5b3ef87c-c96d-4b8f-abff-f5be3f6c75cb
institution University of Oxford
language English
last_indexed 2024-03-06T22:40:04Z
publishDate 2002
record_format dspace
spelling oxford-uuid:5b3ef87c-c96d-4b8f-abff-f5be3f6c75cb2022-03-26T17:20:54ZInterchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.Journal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:5b3ef87c-c96d-4b8f-abff-f5be3f6c75cbEnglishSymplectic Elements at Oxford2002Beljonne, DPourtois, GSilva, CHennebicq, EHerz, LFriend, RScholes, GSetayesh, SMullen, KBredas, JThe energy-transfer processes taking place in conjugated polymers are investigated by means of ultrafast spectroscopy and correlated quantum-chemical calculations applied to polyindenofluorenes end-capped with a perylene derivative. Comparison between the time-integrated luminescence and transient absorption spectra measured in solution and in films allows disentangling of the contributions arising from intrachain and from interchain energy-migration phenomena. Intrachain processes dominate in solution where photoexcitation of the polyindenofluorene units induces a rather slow energy transfer to the perylene end moieties. In films, close contacts between chains favors interchain transport of the excited singlet species (from the conjugated bridge of one chain to the perylene unit of a neighboring one); this process is characterized by a 1-order-of-magnitude increase in transfer rate with respect to solution. This description is supported fully by the results of quantum-chemical calculations that go beyond the usual point-dipole model approximation and account for geometric relaxation phenomena in the excited state before energy migration. The calculations indicate a two-step mechanism for intrachain energy transfer with hopping along the conjugated chains as the rate-limiting step; the higher efficiency of the interchain transfer process is mainly due to larger electronic coupling matrix elements between closely lying chains.
spellingShingle Beljonne, D
Pourtois, G
Silva, C
Hennebicq, E
Herz, L
Friend, R
Scholes, G
Setayesh, S
Mullen, K
Bredas, J
Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title_full Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title_fullStr Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title_full_unstemmed Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title_short Interchain vs. intrachain energy transfer in acceptor-capped conjugated polymers.
title_sort interchain vs intrachain energy transfer in acceptor capped conjugated polymers
work_keys_str_mv AT beljonned interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT pourtoisg interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT silvac interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT hennebicqe interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT herzl interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT friendr interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT scholesg interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT setayeshs interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT mullenk interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers
AT bredasj interchainvsintrachainenergytransferinacceptorcappedconjugatedpolymers