Dithiafulvene derivatized donor-acceptor norbornadienes with redshifted absorption
Artikel i vetenskaplig tidskrift, 2019

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 N has to be moved from the UV to the visible region. Here we show that functionalization of the system with dithiafulvene (DTF) electron donors causes remarkable 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 comes, however, with a drawback with 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 (S 1 ) 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 the future design of N-Q energy storage systems with an improved solar spectrum match.


Mads Mansø

Köpenhamns universitet

Chalmers, Kemi och kemiteknik

Martin Drøhse Kilde

Köpenhamns universitet

Sandeep Kumar Singh

Chalmers, Fysik, Material- och ytteori

Paul Erhart

Chalmers, Fysik, Material- och ytteori

Kasper Moth-Poulsen

Chalmers, Kemi och kemiteknik, Tillämpad kemi

M. B. Nielsen

Köpenhamns universitet

Physical Chemistry Chemical Physics

1463-9076 (ISSN) 1463-9084 (eISSN)

Vol. 21 6 3092-3097


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