Mechanisms of IR amplification in radical cation polarons.
Journal
Chemical science
ISSN: 2041-6520
Titre abrégé: Chem Sci
Pays: England
ID NLM: 101545951
Informations de publication
Date de publication:
22 Jan 2020
22 Jan 2020
Historique:
entrez:
14
6
2021
pubmed:
22
1
2020
medline:
22
1
2020
Statut:
epublish
Résumé
Break down of the Born-Oppenheimer approximation is caused by mixing of electronic and vibrational transitions in the radical cations of some conjugated polymers, resulting in unusually intense vibrational bands known as infrared active vibrations (IRAVs). Here, we investigate the mechanism of this amplification, and show that it provides insights into intramolecular charge migration. Spectroelectrochemical time-resolved infrared (TRIR) and two-dimensional infrared (2D-IR) spectroscopies were used to investigate the radical cations of two butadiyne-linked conjugated porphyrin oligomers, a linear dimer and a cyclic hexamer. The 2D-IR spectra reveal strong coupling between all the IRAVs and the electronic π-π* polaron band. Intramolecular vibrational energy redistribution (IVR) and vibrational relaxation occur within ∼0.1-7 ps. TRIR spectra show that the transient ground state bleach (GSB) and excited state absorption (ESA) signals have anisotropies of 0.31 ± 0.07 and 0.08 ± 0.04 for the linear dimer and cyclic hexamer cations, respectively. The small TRIR anisotropy for the cyclic hexamer radical cation indicates that the vibrationally excited polaron migrates round the nanoring on a time scale faster than the measurement,
Identifiants
pubmed: 34123299
doi: 10.1039/c9sc05717j
pii: c9sc05717j
pmc: PMC8150116
doi:
Types de publication
Journal Article
Langues
eng
Pagination
2112-2120Subventions
Organisme : European Research Council
ID : 320969
Pays : International
Informations de copyright
This journal is © The Royal Society of Chemistry.
Déclaration de conflit d'intérêts
There are no conflicts to declare.
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