Journal article

Authors list: Slavov, C; Yang, C; Heindl, AH; Wegner, HA; Dreuw, A; Wachtveitl, J

Publication year: 2020

Pages: 380-387

Journal: Angewandte Chemie International Edition

Volume number: 59

Issue number: 1

ISSN: 1433-7851

eISSN: 1521-3773

Open access status: Hybrid

DOI Link: https://doi.org/10.1002/anie.201909739

Publisher: Wiley

Abstract: 
Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)- and (Z)-isomer absorption bands, allowing for highly selective photoconversion. The (Z)-isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone-pair pi interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub-ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.

Harvard Citation style: Slavov, C., Yang, C., Heindl, A., Wegner, H., Dreuw, A. and Wachtveitl, J. (2020) Thiophenylazobenzene: an Alternative Photoisomerization Controlled by Lone-Pair⋅⋅⋅π Interaction, Angewandte Chemie International Edition, 59(1), pp. 380-387. https://doi.org/10.1002/anie.201909739

APA Citation style: Slavov, C., Yang, C., Heindl, A., Wegner, H., Dreuw, A., & Wachtveitl, J. (2020). Thiophenylazobenzene: an Alternative Photoisomerization Controlled by Lone-Pair⋅⋅⋅π Interaction. Angewandte Chemie International Edition. 59(1), 380-387. https://doi.org/10.1002/anie.201909739