Stiff-stilbene photoswitch ruptures bonds not by pulling but by local heating

• Verfasst von: Stauch, Tim [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Stiff-stilbene photoswitch ruptures bonds not by pulling but by local heating
• Verf.angabe: Tim Stauch and Andreas Dreuw
• Umfang: 6 S.
• Fussnoten: Gesehen am 08.12.2017
• Titel Quelle: Enthalten in: Physical chemistry, chemical physics
• Jahr Quelle: 2016
• Band/Heft Quelle: 18(2016), 23, S. 15848-15853
• ISSN Quelle: 1463-9084
• DOI: doi:10.1039/C6CP02395A
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1566179416

Abstract

The photochemical cis → trans-isomerization of stiff-stilbene (1-(1-indanyliden)indan) was previously used to trigger the ring opening of cyclobutene, i.e. the retro [2+2] cycloaddition leading to butadiene, mechanically. However, the forces generated by stiff-stilbene during photoisomerization are limited, so it is unclear in how far the mechanical properties of stiff-stilbene determine the efficiency of the bond rupture. Here we present a computational study in which we investigate the mechanochemical properties of this reaction. We show that the mechanical work transmitted from stiff-stilbene to cyclobutene is much too low to account for the observed facilitation of the ring opening. Hence, local heating resulting from the absorption of a photon by stiff-stilbene and efficient non-radiative decay are the key elements initiating this reaction.