Effect of hydrogen-bonding on the excited-state reactivity of fullerene derivatives and its impact on the control of the emission polarisation from photopolic single crystals

Physical Chemistry Chemical Physics : PCCP
Guillaume RaffyDario M Bassani

Abstract

The kinetics of the irreversible photoinduced switch in polarisation (p) observed in single crystals of a fullerene derivative possessing hydrogen-bonding barbiturate units were investigated using confocal fluorescence microscopy. In the samples investigated, it was found that the maximum luminescence polarisation (p = 0.78) is obtained for an orientation of ca. 60° from the long axis of the crystal. Upon irradiation at 385 nm, the maximum luminescence polarisation undergoes a rotation of ca. 70° with respect to the initial orientation and reaches a new value of p = 0.40. The results indicate that the process is not dependent on the orientation of the incident polarised excitation beam and that it is not accompanied by a noticeable change in the photophysical properties of the crystal. Based on these observations, a mechanism is proposed in which photoinduced dimerisation occurs from the lowest energy emissive excimer-like state that acts as a sink for the excitation energy.

References

Oct 15, 1969·Acta Crystallographica. Section B, Structural Science·B M CravenM M Rodrigues
Apr 4, 2002·Proceedings of the National Academy of Sciences of the United States of America·Shinya InouéP T Tran
Oct 23, 2003·Journal of the American Chemical Society·Nathan D McClenaghanDario M Bassani
Dec 24, 2003·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Vincent DarcosDario M Bassani
Dec 22, 2005·Journal of the American Chemical Society·André Del GuerzoJean-Pierre Desvergne
Oct 27, 2006·The Journal of Organic Chemistry·Yann MolardJames H R Tucker
Jun 15, 2007·Journal of the American Chemical Society·Lars PoulsenJohannes Gierschner

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Citations

Nov 5, 2015·Faraday Discussions·Alejandro Méndez-Ardoy, Dario M Bassani

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