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Controlling Intramolecular Singlet Fission Dynamics via Torsional Modulation of Through-Bond versus Through-Space Couplings

Majumder, K and Mukherjee, S and Panjwani, NA and Lee, J and Bittl, R and Kim, W and Patil, S and Musser, AJ (2023) Controlling Intramolecular Singlet Fission Dynamics via Torsional Modulation of Through-Bond versus Through-Space Couplings. In: Journal of the American Chemical Society, 145 (38). 20883 -20896.

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Official URL: https://pubs.acs.org/doi/pdf/10.1021/jacs.3c06075?...


Covalent dimers, particularly pentacenes, are the dominant platform for developing a mechanistic understanding of intramolecular singlet fission (iSF). Numerous studies have demonstrated that a photoexcited singlet state in these structures can rapidly and efficiently undergo exciton multiplication to form a correlated pair of triplets within a single molecule, with potential applications from photovoltaics to quantum information science. One of the most significant barriers limiting such dimers is the fast recombination of the triplet pair, which prevents spatial separation and the formation of long-lived triplet states. There is an ever-growing need to develop general synthetic strategies to control the evolution of triplets following iSF and enhance their lifetime. Here, we rationally tune the dihedral angle and interchromophore separation between pairs of pentacenes in a systematic series of bridging units to facilitate triplet separation. Through a combination of transient optical and spin-resonance techniques, we demonstrate that torsion within the linker provides a simple synthetic handle to tune the fine balance between through-bond and through-space interchromophore couplings that steer iSF. We show that the full iSF pathway from femtosecond to microsecond timescales is tuned through the static coupling set by molecular design and structural fluctuations that can be biased through steric control. Our approach highlights a straightforward design principle to generate paramagnetic spin pair states with higher yields. © 2023 American Chemical Society

Item Type: Journal Article
Publication: Journal of the American Chemical Society
Publisher: American Chemical Society
Additional Information: The copyright for this article belongs to the American Chemical Society.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 03 Dec 2023 09:10
Last Modified: 03 Dec 2023 09:10
URI: https://eprints.iisc.ac.in/id/eprint/83469

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