ArticleChemical science2020
Mechanisms of IR amplification in radical cation polarons.
Article in Chemical science, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 8 papers.
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Who cites it
8 citing papers in PubMed.
- Recent Advances in Probing Electron Delocalization in Conjugated Molecules by Attached Infrared Reporter Groups for Energy Conversion and Storage.ACS applied energy materials · 2025Review
- Radical Anions of Porphyrin Molecular Wires: Delocalization and Dynamics.Journal of the American Chemical Society · 2025Article
- Evaluating the interactions between vibrational modes and electronic transitions using frontier orbital energy derivatives.Chemical communications (Cambridge, England) · 2024Article
- Nitrile Substituents at the Conjugated Dipyridophenazine Moiety as Infrared Redox Markers in Electrochemically Reduced Heteroleptic Ru(II) Polypyridyl Complexes.Inorganic chemistry · 2024Article
- Real-Time Tracking of Hot Carrier Injection at the Interface of FAPbBrACS central science · 2024Article
- Unraveling Excited State Dynamics of a Single-Stranded DNA-Assembled Conjugated Polyelectrolyte.The journal of physical chemistry letters · 2023Article
- Population and coherence dynamics in large conjugated porphyrin nanorings.Chemical science · 2022Article
- IR linewidth and intensity amplifications of nitrile vibrations report nuclear-electronic couplings and associated structural heterogeneity in radical anions.Chemical science · 2021Article
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Authors and funding
9 authors.
Funding
Abstract
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,
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