Issue 43, 2024

Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers

Abstract

An array of thiophene-based π-conjugated linkers in covalently linked pentacene dimers allow us to access diverse quantum interference (QI), modulating nonadiabatic coupling (NAC) in the singlet fission (SF) process. Simulations show that structural isomerism in terms of S atom orientation substantially alters NAC with relatively marginal impacts on energies. Extended curly arrow rules (ECARs) reveal sensitive dependence of QI on SF linker topologies and connectivity, categorizing regimes of constructive, destructive, and previously unrealized in SF research, shifted destructive QI. Drastic NAC changes in terms of S atom orientation are rationalized based on the nature of QI. Our results from nonequilibrium Green's function calculation using density functional theory corroborate the classification of QI regimes based on ECARs. Moreover, we found that the extent of charge resonance contribution in electronic states relevant to multiexciton formation and the appearance of optically allowed charge transfer excitation strongly depends on the operative QI regime. Notably, the magnitude of NAC effectively captures this influence. Our findings show that QI can rationalize and semi-quantitatively correlate with NAC for the multiexciton formation step in the SF process.

Graphical abstract: Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers

Supplementary files

Article information

Article type
Edge Article
Submitted
30 May 2024
Accepted
02 Oct 2024
First published
09 Oct 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 17823-17830

Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers

J. Lee, S. Eom and H. Kim, Chem. Sci., 2024, 15, 17823 DOI: 10.1039/D4SC03546A

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