Photochemical dynamics of E-methylfurylfulgide—kinematic effects on photorelaxation dynamics of furylfulgides

Schönborn, Jan Boyke; Hartke, Bernd

doi:10.1039/c3cp53495b

Cited by 22 publications

(31 citation statements)

References 35 publications

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“…The scenario is further supported by recent state-averaged CASSCF/CASPT2 calculations for photo-excited Z-MeF, where converged S 1 -S 0 CI structures could be obtained. 24 The distinctive feature of the CI structures is a twist along the C 4 QC 5 double bond corresponding to a dihedral angle of 901 in line with the scenario suggested above. The proposed direct photoisomerisation of Z-fulgides differs from the accepted model for the E -Z photoisomerisation of unpolar polyenes including This is © the Owner Societies 2014 hexatriene (HT) via an optically dark intermediate state, [36][37][38][39][40][41][42][43][44][45] but is in line with the suggested situation for biomimetic dipolar NAIP photoswitches, where the photo-excited state is zwitterionic.…”

Section: Photoisomerisation Pathwayssupporting

confidence: 71%

“…Previous experimental and theoretical studies the selected fulgide derivatives were able to relate the observed significant changes in the photoswitching behaviour of the respective E-and C-isomers to details of the ultrafast photo-induced dynamics affected by steric constraints at the central HT unit, intramolecular bridging, or by extension of the p-electron system of the furyl unit. 10,16,[19][20][21][22][23][24] However, the only apparent effect of the structural modifications for the photo-excited Z-fulgides is a moderate slowing of the excited-state dynamics, with time constants ranging from t 1 = 0.18 ps for Z-MeF to t 1 = 0.32 ps for Z-MeBF. The very similar results for all four photo-excited Z-isomers indicate that the underlying Z -E photoisomerisation mechanism remains unaltered by the structural changes.…”

Section: Effects Of Structural Modificationsmentioning

confidence: 99%

“…Extensive work using ultrafast spectroscopy performed in our group for fulgides with selected structural motifs 10,[16][17][18][19][20] (see Fig. 1b) and quantum chemical calculations [21][22][23][24] related the trends in photochemical behaviour upon structural variation to details of the underlying ultrafast photo-induced dynamics. Based on the experimental results, intramolecular bridging was introduced as a new structural motif to increase the quantum yields of the desired ring closure and block the E -Z isomerisation.…”

Section: Introductionmentioning

confidence: 99%

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Ultrafast Z → E photoisomerisation of structurally modified furylfulgides

Renth

Siewertsen

Strübe

et al. 2014

Phys. Chem. Chem. Phys.

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Femtosecond broadband transient absorption spectroscopy has been used in a comparative study of the ultrafast photo-induced Z → E isomerisation reactions of four photochromic furylfulgides with selected structural motifs in n-hexane as solvent. The results show that all studied Z-fulgides exhibit fast and direct processes along barrierless excited-state pathways involving a conical intersection (CI) between the S1 and S0 electronic states. The excited-state lifetimes range from τ1 = 0.18 ps for the methyl derivative to τ1 = 0.32 ps for the benzofurylfulgide. The impulsive rise of the absorption by vibrationally hot Z- and E-isomers back in the electronic ground state following electronic deactivation and isomerisation indicates that the initially prepared wave packet persists even after passage of the CI. Furthermore, the results provide qualitative evidence for a quickly dephasing vibrational coherence in the electronic ground state. In contrast to the significant changes observed for the corresponding E- and C-isomers [Renth et al., Int. Rev. Phys. Chem., 2013, 32, 1-38], the excited-state dynamics of the Z-isomers is not affected by varied sterical hindrance from methyl and isopropyl substituents at the central hexatriene unit, or by intramolecular bridging, and remains unaltered upon extension of the π-electron system in a benzannulated furyl fulgide.

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Section: Photoisomerisation Pathwayssupporting

confidence: 71%

Section: Effects Of Structural Modificationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Ultrafast Z → E photoisomerisation of structurally modified furylfulgides

Renth

Siewertsen

Strübe

et al. 2014

Phys. Chem. Chem. Phys.

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“…The final evaluations are done for 967, 1013, 1045, and 856 trajectories of SPc, SPt, SPmc, and SPmt that are finished successfully in the photodynamics runs. Further technical details are given in previous publications. − …”

Section: Computational Detailsmentioning

confidence: 99%

Nonadiabatic Dynamics Simulations on Early-Time Photochemistry of Spirobenzopyran

et al. 2020

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Photoinduced ring-opening, decay, and isomerization of spirobenzopyran have been explored by the OM2/MRCI nonadiabatic dynamics simulations based on Tully’s fewest-switches surface hopping scheme. The efficient S1 to S0 internal conversion as observed in experiments is attributed to the existence of two efficient excited-state decay pathways. The first one is related to the C–N dissociation, and the second one is done to the C–O dissociation. The C–O dissociation pathway is dominant, and more than 90% trajectories decay to the S0 state via the C–O bond-fission related S1/S0 conical intersections. Near these regions in the S0 state, trajectories can either return to spirobenzopyran or proceed to various intermediates including merocyanine via a series of bond rotations. Our nonadiabatic dynamics simulations also demonstrate that the hydrogen-out-of-plane (HOOP) motion is important for efficient and ultrafast excited-state deactivation. On the other hand, we have also found that the replacement of methyl groups by hydrogen atoms in spirobenzopyran can artificially introduce different intramolecular hydrogen transfers leading to hydrogen-transferred intermediates. This finding is important for the community and demonstrates that such a kind of structural truncation, sometimes, could be problematic, leading to incorrect photodynamics. Our present work provides valuable insights into the photodynamics of spirobenzopyran, which could be helpful for the design of spiropyran-based photochromic materials.

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“…85 Further technical details are given in previous publications. [86][87][88][89][90][91][92][93][94][95]…”

Section: Computational Detailsmentioning

confidence: 99%

Stereoselective Excited-State Isomerization and Decay Paths in cis-Cyclobiazobenzene

Zhang

Qiu

et al. 2019

J. Phys. Chem. A

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Herein we have employed OM2/MRCI-based full-dimensional nonadiabatic dynamics simulations to explore the photoisomerization and subsequent excited-state decay of a macrocyclic cyclobiazobenzene (CBA) molecule. Two S1/S0 conical intersection structures are found to be responsible for the excited-state decay. Related to these two conical intersections, we found two stereoselective photoisomerization and excited-state decay pathways, which correspond to the clockwise and counterclockwise rotation motions with respect to the N=N bond of the azo group. In both pathways the excited-state isomerization is ultrafast and finishes within ca. 69 fs; but, the clockwise isomerization channel is much more favorable than the counterclockwise one with a ratio of 74% vs. 26%. Importantly, the present work demonstrates that stereoselective pathways exist not only in the photoisomerization of isolated azobenzene-like systems but also in macrocyclic systems with multiple azobenzenes (ABs). This finding could provide useful insights for understanding and controlling the photodynamics of macrocyclic nanostructures with AB units as the main building units.

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Photochemical dynamics of E-methylfurylfulgide—kinematic effects on photorelaxation dynamics of furylfulgides

Cited by 22 publications

References 35 publications

Ultrafast Z → E photoisomerisation of structurally modified furylfulgides

Ultrafast Z → E photoisomerisation of structurally modified furylfulgides

Nonadiabatic Dynamics Simulations on Early-Time Photochemistry of Spirobenzopyran

Stereoselective Excited-State Isomerization and Decay Paths in cis-Cyclobiazobenzene

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