Geometries and Terahertz Motions Driving Quintet Multiexcitons and Ultimate Triplet-Triplet Dissociations via the Intramolecular Singlet Fissions

Yasuhiro Kobori, Masaaki Fuki, Shunta Nakamura, Taku Hasobe

Research output: Contribution to journalArticlepeer-review

Abstract

Importance of vibronic effects has been highlighted for the singlet-fission (SF) that converts one high-energy singlet exciton into doubled triplet excitons, as strongly coupled multiexcitons. However, molecular mechanisms of spin conversion processes and ultimate decouplings in the multiexcitons are poorly understood. We have analyzed geometries and exchange couplings (singlet-quintet energy gaps: 6J) of the photoinduced multiexcitons in the pentacene dimers bridged by a phenylene at ortho and meta positions [denoted as o-(Pc)2 and m-(Pc)2] by simulations of the time-resolved electron paramagnetic resonance spectra. We clarified that terahertz molecular conformation dynamics play roles on the spin conversion from the singlet strongly coupled multiexcitons 1(TT) to the quintet multiexcitons 5(TT) and on the intramolecular decouplings in the 6J to form spin correlated triplet pairs (T+T). The strongly coupled 5(TT) multiexcitons are revealed to possess entirely planar conformations stabilized by mutually delocalized spin distributions, while the intramolecular decoupled spin-correlated triplet pairs generated at 1 μs are also stabilized by distorted conformations resulting in two separately localized biradical characters.

Original languageEnglish
Pages (from-to)9411-9419
Number of pages9
JournalJournal of Physical Chemistry B
Volume124
Issue number42
DOIs
Publication statusPublished - 2020 Oct 22

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Geometries and Terahertz Motions Driving Quintet Multiexcitons and Ultimate Triplet-Triplet Dissociations via the Intramolecular Singlet Fissions'. Together they form a unique fingerprint.

Cite this