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Issue 34, 2014
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New insights into the by-product fatigue mechanism of the photo-induced ring-opening in diarylethenes

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Abstract

The photochromic properties of diarylethenes, some of the most studied class of molecular switches, are known to be controlled by non-adiabatic decay at a conical intersection seam. Nevertheless, as their fatigue-reaction mechanism – leading to non-photochromic products – is yet to be understood, we investigate the photo-chemical formation of the so-called by-product isomer using three complementary computational methods (MMVB, CASSCF and CASPT2) on three model systems of increasing complexity. We show that for the ring-opening reaction a transition state on S1(2A) involving bond breaking of the penta-ring leads to a low energy S1(2A)/S0(1A) conical intersection seam, which lies above one of the transition states leading to the by-product isomer on the ground state. Therefore, radiationless decay and subsequent side-product formation can take place explaining the photo-degradation responsible for the by-product generation in diarylethene-type molecules. The effect of dynamic electron correlation and the possible role of inter-system crossing along the penta-ring opening coordinate are discussed as well.

Graphical abstract: New insights into the by-product fatigue mechanism of the photo-induced ring-opening in diarylethenes

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Publication details

The article was received on 09 Jul 2014, accepted on 16 Jul 2014 and first published on 18 Jul 2014


Article type: Paper
DOI: 10.1039/C4CP03001J
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Citation: Phys. Chem. Chem. Phys., 2014,16, 18463-18471
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    New insights into the by-product fatigue mechanism of the photo-induced ring-opening in diarylethenes

    D. Mendive-Tapia, A. Perrier, M. J. Bearpark, M. A. Robb, B. Lasorne and D. Jacquemin, Phys. Chem. Chem. Phys., 2014, 16, 18463
    DOI: 10.1039/C4CP03001J

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