Stiff-stilbene photoswitch ruptures bonds not by pulling but by local heating
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...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
27 May 2016
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| In: |
Physical chemistry, chemical physics
Year: 2016, Volume: 18, Issue: 23, Pages: 15848-15853 |
| ISSN: | 1463-9084 |
| DOI: | 10.1039/C6CP02395A |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1039/C6CP02395A Verlag, Volltext: http://pubs.rsc.org/en/content/articlelanding/2016/cp/c6cp02395a 
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| Author Notes: | Tim Stauch and Andreas Dreuw |
| Summary: | 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. |
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| Item Description: | Gesehen am 08.12.2017 |
| Physical Description: | Online Resource |
| ISSN: | 1463-9084 |
| DOI: | 10.1039/C6CP02395A |