Excited state dynamics and conjugation effects of the photoisomerization reactions of dihydroazulene
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Excited state dynamics and conjugation effects of the photoisomerization reactions of dihydroazulene. / Hillers-Bendtsen, Andreas Erbs; Kjeldal, Frederik Ørsted; Ree, Nicolai; Matito, Eduard; Mikkelsen, Kurt V.
I: Physical Chemistry Chemical Physics, Bind 24, Nr. 47, 2022, s. 28934-28943.Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › fagfællebedømt
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TY - JOUR
T1 - Excited state dynamics and conjugation effects of the photoisomerization reactions of dihydroazulene
AU - Hillers-Bendtsen, Andreas Erbs
AU - Kjeldal, Frederik Ørsted
AU - Ree, Nicolai
AU - Matito, Eduard
AU - Mikkelsen, Kurt V.
N1 - Publisher Copyright: © 2022 The Royal Society of Chemistry.
PY - 2022
Y1 - 2022
N2 - Herein, we present an investigation of the excited state dynamics of the dihydroazulene photoswitch and its photoinduced reaction to vinylheptafulvene. The focus is on how the introduction of a benzannulated ring in different sites of the structure can modify the excited state topology and thus the kinetics of the ring opening reaction of DHA by alteration of the excited state conjugation of the system. The dynamics of the systems is obtained utilizing ab initio density functional theory calculations in different solvents coupled with unimolecular reaction theory. To accompany these results, the electron delocalization is investigated using the quantum theory of atoms in molecules partitioning to follow the trends induced by the benzannulated ring. It is observed that the introduction of a benzannulated ring can both enhance and diminish the rate of the photoinduced ring opening of dihydroazulene and that certain patterns of conjugation are consistent with the rate constants. Lastly, we find good agreement with earlier experimental studies indicating that the chosen approach could be used to predict whether photochromic systems lose their photoswitchability upon being optimized for specific applications via functionalization.
AB - Herein, we present an investigation of the excited state dynamics of the dihydroazulene photoswitch and its photoinduced reaction to vinylheptafulvene. The focus is on how the introduction of a benzannulated ring in different sites of the structure can modify the excited state topology and thus the kinetics of the ring opening reaction of DHA by alteration of the excited state conjugation of the system. The dynamics of the systems is obtained utilizing ab initio density functional theory calculations in different solvents coupled with unimolecular reaction theory. To accompany these results, the electron delocalization is investigated using the quantum theory of atoms in molecules partitioning to follow the trends induced by the benzannulated ring. It is observed that the introduction of a benzannulated ring can both enhance and diminish the rate of the photoinduced ring opening of dihydroazulene and that certain patterns of conjugation are consistent with the rate constants. Lastly, we find good agreement with earlier experimental studies indicating that the chosen approach could be used to predict whether photochromic systems lose their photoswitchability upon being optimized for specific applications via functionalization.
U2 - 10.1039/d2cp02706b
DO - 10.1039/d2cp02706b
M3 - Journal article
C2 - 36416446
AN - SCOPUS:85142756521
VL - 24
SP - 28934
EP - 28943
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 47
ER -
ID: 328234944