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Dithiafulvene derivatized donor-acceptor norbornadienes with redshifted absorption

Abstract

Photoisomerization of norbornadiene (N) to its metastable isomer quadricyclane (Q) has attracted interest as a strategy for harvesting and storing solar energy. For this strategy to mature the absorption maximum of the N has to be moved from the UV to visible region. Here we show that functionalization of the system with dithiafulvene (DTF) electron donors causes remarkabe redshifts of various N derivatives. Thus, some derivatives were found to absorb light with an absorption onset up to 556 nm. The incorporation of DTF units come, however, with a drawback in regard to achieving reversible N-to-Q and Q-to-N isomerizations. For some derivatives, the photoisomerization was completely quenched. The compounds were subjected to a computational study to shed light on the underlying reason for this reluctance to undergo photoisomerization. The computational study revealed that in these systems, the first excited state (S1) is positioned close to or lower than the transition state for photoconversion, effectively blocking a possible conversion to Q, thus revealing a practical challenge for future design of N-Q energy storage systems with improved solar spectrum match.

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Publication details

The article was received on 19 Dec 2018, accepted on 09 Jan 2019 and first published on 10 Jan 2019


Article type: Paper
DOI: 10.1039/C8CP07744D
Citation: Phys. Chem. Chem. Phys., 2019, Accepted Manuscript
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    Dithiafulvene derivatized donor-acceptor norbornadienes with redshifted absorption

    M. Mansø, M. D. Kilde, S. K. Singh, P. Erhart, K. Moth-Poulsen and M. B. Nielsen, Phys. Chem. Chem. Phys., 2019, Accepted Manuscript , DOI: 10.1039/C8CP07744D

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