The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers

Ryo Hayasaka, Hayato Sakai, Masaaki Fuki, Tsubasa Okamoto, Ramsha Khan, Masahiro Higashi, Nikolai V. Tkachenko, Yasuhiro Kobori, Taku Hasobe

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Abstract

A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high-yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.

Original languageEnglish
JournalAngewandte Chemie - International Edition
Volume63
Issue number8
DOIs
Publication statusE-pub ahead of print - 5 Jan 2024
Publication typeA1 Journal article-refereed

Keywords

  • Ferrocene
  • Multiexciton Formation
  • Pentacene
  • Rotational Motion
  • Singlet Fission

Publication forum classification

  • Publication forum level 3

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry

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