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"Molecular model of the ring-opening and ring-closure reaction of a fluorinated indolylfulgide" Artur Nenov, Wolfgang J. Schreier, Florian O. Koller, Markus Braun, Regina de Vivie-Riedle, Wolfgang Zinth, Igor PugliesiJ. Phys. Chem. A, 116, 10518-10528 (2012) Abstract: A combination of experimental and theoretical techniques is used to study the photoinduced ring-opening/closure of a trifluoromethyl-indolylfulgide. Time resolved UV/Vis pump and IR probe measurements are performed in the sub-picosecond to 50 ps time range. Probing in the mid IR between 1200 cm-1 and 1900 cm-1 provides mode-specific dynamics and reveals pho-tochemical reaction dynamics as well as the presence of a non-cyclizable conformer. Ring opening occurs with about 3 ps. Experiments on the open isomer confirm that the ring-closure occurs on the sub-picosecond time scale. They also show a 10 ps transient that can be as-signed to internal conversion of a non-cyclizable conformer. Quantum chemical calculations with multi-reference methods are used to explore the complex potential energy landscape in the excited electronic state showing paths for ring-opening and closure reactions as well as for competing side-reactions. The calculations reveal that photoexcitation induces a charge trans-fer from the indole to the anhydride. The same charge transfer drives the system towards a low-energy CoIn seam spreading from the closed to the open ring side and is responsible for the ultrafast relaxation to the ground state. The ultrafast photoreactivity comes at the expense of selectivity. BMO authors (in alphabetic order): Markus Braun Florian Koller Igor Pugliesi Tobias Schrader Wolfgang Zinth  WWW-Version |
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Letzte Änderung: 2016-09-14 13:34
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