Quantum interference effects elucidate triplet-pair formation dynamics in intramolecular singlet-fission molecules

Kaia R. Parenti, Rafi Chesler, Guiying He, Pritam Bhattacharyya, Beibei Xiao, Huaxi Huang, Daniel Malinowski, Jocelyn Zhang, Xiaodong Yin, Alok Shukla, Sumit Mazumdar, Matthew Y. Sfeir, Luis M. Campos

Research output: Contribution to journalArticlepeer-review

11 Scopus citations

Abstract

Quantum interference (QI)—the constructive or destructive interference of conduction pathways through molecular orbitals—plays a fundamental role in enhancing or suppressing charge and spin transport in organic molecular electronics. Graphical models were developed to predict constructive versus destructive interference in polyaromatic hydrocarbons and have successfully estimated the large conductivity differences observed in single-molecule transport measurements. A major challenge lies in extending these models to excitonic (photoexcited) processes, which typically involve distinct orbitals with different symmetries. Here we investigate how QI models can be applied as bridging moieties in intramolecular singlet-fission compounds to predict relative rates of triplet pair formation. In a series of bridged intramolecular singlet-fission dimers, we found that destructive QI always leads to a slower triplet pair formation across different bridge lengths and geometries. A combined experimental and theoretical approach reveals the critical considerations of bridge topology and frontier molecular orbital energies in applying QI conductance principles to predict rates of multiexciton generation. [Figure not available: see fulltext.]

Original languageEnglish (US)
Pages (from-to)339-346
Number of pages8
JournalNature Chemistry
Volume15
Issue number3
DOIs
StatePublished - Mar 2023

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering

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