Switching between coherent and incoherent singlet fission via solvent-induced symmetry-breaking.
Fuemmeler, Eric G
Chin, Alex W
Musser, Andrew J
Journal of the American Chemical Society
American Chemical Society
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Alvertis, A., Lukman, S., Hele, T., Fuemmeler, E. G., Feng, J., Wu, J., Greenham, N., et al. (2019). Switching between coherent and incoherent singlet fission via solvent-induced symmetry-breaking.. Journal of the American Chemical Society https://doi.org/10.1021/jacs.9b05561
Singlet fission in organic semiconductors causes a singlet exciton to decay into a pair of triplet excitons and holds potential for increasing the efficiency of photovoltaic devices. In this combined experimental and theoretical study, we reveal that a covalent dimer of the organic semiconductor tetracene undergoes activated singlet fission by qualitatively different mechanisms depending on the solvent environment. We show that intramolecular vibrations are an integral part of this mechanism, giving rise to mixing between charge transfer and triplet pair excitations. Both coherent or incoherent singlet fission can occur, depending on transient solvent-induced energetic proximity between the states, giving rise to complex variation of the singlet fission mechanism and timescale in the different environments. Our results suggest a more general principle for controlling the efficiency of photochemical reactions by utilizing transient interactions to tune the energetics of reactant and product states and switch between incoherent and coherent dynamics.
This work was supported by the Engineering and Physical Sciences Research Council, UK (grant numbers EP/L015552/1, EP/M025330/1 and EP/M005143/1). A.M.A. acknowledges the support of the Winton Programme for the Physics of Sustainability. S.L. thanks A*STAR Graduate Scholarship support from A*STAR Singapore. T.J.H.H. acknowledges a Research Fellowship from Jesus College, Cambridge. E.G.F. acknowledges financial support from the National Science Foundation Award No. CHE-1555205. J. W. acknowledges financial support from the MOE Tier 3 programme (MOE2014-T3-1-004).
External DOI: https://doi.org/10.1021/jacs.9b05561
This record's URL: https://www.repository.cam.ac.uk/handle/1810/298060
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