Tuning of switching properties and excited-state dynamics of fulgides by structural modifications

Siewertsen R, Strübe F, Mattay J, Renth F, Temps F (2011)
Physical Chemistry Chemical Physics 13(9): 3800-3808.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The ultrafast photo-induced dynamics of the E-isomers of four selected photochromic fulgides with distinct structural motifs have been elucidated by femtosecond broadband transient absorption spectroscopy in n-hexane as solvent. E -> C and E -> Z isomerisations, respectively, with time constants of similar to 0.12 +/- 0.02 ps and similar to 0.34 +/- 0.03 ps taking place in parallel were found for derivatives with a methyl substituent at the central hexatriene (HT) unit. In contrast, fulgides with increased steric constraints by an iso-propyl substituent or by intramolecular bridging displayed virtually zero E -> Z isomerisation, but instead a desired accelerated and more efficient ring closure in a reaction time of only similar to 50 +/- 10 fs. Both photoisomerisations appear to follow excited-state pathways with distinctive conical intersections. For the ring closure, direct barrierless pathways with steep downhill gradients are likely. Furthermore, the results indicate conformer-specific reactions, with ring closure exclusively by the E-alpha conformer and E -> Z isomerisation predominantly by the E-beta conformer, because the E-alpha -> Z channel is unfavoured by the faster and kinetically more competitive E-alpha -> C reaction. DFT calculations of the equilibrium structures showed that the sterically demanding groups at the HT unit shift the conformer equilibria towards the E-alpha conformers. At the same time, they appear to cause a favourable pre-orientation of the furyl unit that accelerates the conrotatory ring closure in the E-alpha -> C reaction. Benzo-annulation of the furyl unit has little effect on the observed dynamics. Overall, the results demonstrate how the excited-state dynamics and thereby the photoswitching properties of fulgides can be successfully tuned and improved by structural modifications at the chromophores.
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Physical Chemistry Chemical Physics
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13
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9
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3800-3808
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Siewertsen R, Strübe F, Mattay J, Renth F, Temps F. Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics. 2011;13(9):3800-3808.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., & Temps, F. (2011). Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics, 13(9), 3800-3808. doi:10.1039/c0cp01890b
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., and Temps, F. (2011). Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics 13, 3800-3808.
Siewertsen, R., et al., 2011. Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics, 13(9), p 3800-3808.
R. Siewertsen, et al., “Tuning of switching properties and excited-state dynamics of fulgides by structural modifications”, Physical Chemistry Chemical Physics, vol. 13, 2011, pp. 3800-3808.
Siewertsen, R., Strübe, F., Mattay, J., Renth, F., Temps, F.: Tuning of switching properties and excited-state dynamics of fulgides by structural modifications. Physical Chemistry Chemical Physics. 13, 3800-3808 (2011).
Siewertsen, Ron, Strübe, Frank, Mattay, Jochen, Renth, Falk, and Temps, Friedrich. “Tuning of switching properties and excited-state dynamics of fulgides by structural modifications”. Physical Chemistry Chemical Physics 13.9 (2011): 3800-3808.

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