Theoretical Study on the Photochromic Cycloreversion Reactions of Dithienylethenes; on the Role of the Conical Intersections

Asano, Yukako; Murakami, Akinori; Kobayashi, Takao; Goldberg, Alexander; Guillaumont, Dominique; Yabushita, Satoshi; Irie, Masahiro; Nakamura, Shinichiro

doi:10.1021/ja035035o

Cited by 121 publications

(143 citation statements)

References 36 publications

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“…The errors in the time constants from the global fits are $10%. Because of the close resemblance in spectral shape of the levels involved in the model, the different time constants cannot be directly linked to a physical process, however, comparison with previous studies is strongly suggestive of certain underlying processes [10][11][12][13][14]. The subpicosecond time constant observed in our data corresponds well with a time constant assigned to the initial decay of the excited state by level crossing (1B-2A) in cyclohexadiene, the core of the dithienylethene molecular switches.…”

Section: Resultssupporting

confidence: 75%

Photoswitchable molecular wires: From a sexithiophene to a dithienylethene and back

Milder

Areephong

Feringa

et al. 2009

Chemical Physics Letters

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a b s t r a c tPhotoswitchable dithienylethene groups, added to both a-ends of a sexithiophene molecular wire, switch reversibly between their open and closed forms upon irradiation. The open form has an excited state lifetime of 500 ps and is highly fluorescent, as is typical for oligothiophenes. In contrast the closed form is non-fluorescent and the excited state lifetime is a shorter by a factor of 100, reminiscent of a dithienylethene. In this system, we control the fundamental character of a molecular system through optical switching; toggling between a sexithiophene molecular wire and a dithienylethene reversibly.

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Section: Resultssupporting

confidence: 75%

Photoswitchable molecular wires: From a sexithiophene to a dithienylethene and back

Milder

Areephong

Feringa

et al. 2009

Chemical Physics Letters

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“…Of course, this diagram agrees with WÀH rules (but not with WÀH's correlation diagram method). 5,6 Furthermore, recent studies 28 have yielded correlations similar to ours by using the complicated treatments of \avoided crossing" or \conical intersection." It may be worth noting that Lowry and Richardson 49 have proposed the diagram to which the noncrossing rule is applied.…”

Section: The Interconversions Between Hexatriene and Cyclohexadienessupporting

confidence: 72%

Quantization of Chemical Reaction: The Dynamic Correlation Diagram Method Free From Noncrossing Rule

Nohira

2012

J. Theor. Comput. Chem.

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Both Fukui's frontier orbital (FO) theory and WoodwardÀHoffmann's orbital symmetry conservation (WÀH) theory are based on the molecular orbital theory. However, there are some obvious inconsistencies between the two theories in explaining the electron movement. The process of chemical reactions has been explained by the potential surface analysis based on the time-independent Schr€ odinger equation. However, this approach is not always appropriate for describing unsteady states, because the variable of reaction coordinate should be time t by its very nature. When considering the time-scale of chemical reactions for molecules, there is inherent uncertainty in the energy levels for the midway state of chemical reactions owing to the Heisenberg uncertainty principle. The states which can be accurately described by quantum mechanics exist discontinuously in chemical reactions. Such quantization of chemical reactions solves all noncrossing problems. We also show that such an essential fact leads to new concepts and theories in chemical reactions such as stable molecule, elementary reaction and minimum deformation of orbital phases. Finally, taking the regularity in organic reactions as an example, we demonstrate that FO theory and WÀH theory can be unified consistently by the universally applicable \dynamic correlation diagram method."

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“…2) with other first principle studies 11, 19, 30–32 strengthen its reliability, such as huge ground energy barrier, activation energy on first excited PES during ring-opening, barrierless first excited PES during ring-closing, and no-crossing between first and second excited PESs. These no-crossing PESs are also demonstrated in Figure S2 by equation of motion coupled-cluster singles and doubles (EOM-CCSD) method 33 which involves double excitation operator.…”

Section: Resultsmentioning

confidence: 73%

Light penetration-coupled photoisomerization modeling for photodeformation of diarylethene single crystal: upscaling isomerization to macroscopic deformation

Kim

Yun

Cho

2017

Sci Rep

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Diarylethene is one of the photo-responsive materials that show rapid and reversible changes in their color/electrochemical properties and macroscopic deformations in the crystalline phase by light irradiation. Photoisomerization is the main cause of the photo reactivity of diarylethene, and we established a statistical model based on the density matrix formalism, which predicts quantitative isomerization progress as a population term. The model reflects photo-switching properties of the target molecule, which were characterized by first principle calculations, and external stimulus factors (light irradiation conditions and temperature). By merging light penetration physics with the model, we derived light penetration depth dependent isomerization progress to theoretically investigate photodeformation of single crystal. The model well reproduced in-plane shear deformation under ultraviolet light irradiation which would provide guideline for photoactuator design. In addition, the statistical model addressed crucial findings (primary stimuli and molecular design parameter for increasing the isomerization rate, external stimuli enhancing fluorescence performance) itself.

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Theoretical Study on the Photochromic Cycloreversion Reactions of Dithienylethenes; on the Role of the Conical Intersections

Cited by 121 publications

References 36 publications

Photoswitchable molecular wires: From a sexithiophene to a dithienylethene and back

Photoswitchable molecular wires: From a sexithiophene to a dithienylethene and back

Quantization of Chemical Reaction: The Dynamic Correlation Diagram Method Free From Noncrossing Rule

Light penetration-coupled photoisomerization modeling for photodeformation of diarylethene single crystal: upscaling isomerization to macroscopic deformation

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