Quantum yields and potential energy surfaces: a theoretical study

Nakamura, Shinichiro; Kobayashi, Takao; Takata, Atsushi; Uchida, Kôji; Asano, Yukako; Murakami, Akinori; Goldberg, Alexander; Guillaumont, Dominique; Yokojima, Satoshi; Kobatake, Seiya; Irie, Masahiro

doi:10.1002/poc.1245

Cited by 55 publications

(73 citation statements)

References 23 publications

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“…25–27) The energy profile of the potential surface is shown in Fig. 5 as a function of the internuclear distance (q) between two reactive carbons.…”

Section: Theoretical Studymentioning

confidence: 99%

Photochromism of diarylethene molecules and crystals

Irie

2010

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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100

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Photochromism is defined as a reversible transformation of a chemical species between two isomers upon photoirradiation. Although vast numbers of photochromic molecules have been so far reported, photochromic molecules which exhibit thermally irreversible photochromic reactivity are limited to a few examples. The thermal irreversibility is an indispensable property for the application of photochromic molecules to optical memories and switches. We have developed a new class of photochromic molecules named “diarylethenes”, which show the thermally irreversible photochromic reactivity. The well designed diarylethene derivatives provide outstanding photochromic performance: both isomers are thermally stable for more than 470,000 years, photoinduced coloration/decoloration can be repeated more than 105 cycles, the quantum yield of cyclization reaction is close to 1 (100%), and the response times of both coloration and decoloration are less than 10 ps. This review describes theoretical background of the photochromic reactions, color changes of the derivatives in solution as well as in the single crystalline phase, and application of the crystals to light-driven actuators.

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“…25–27) The energy profile of the potential surface is shown in Fig. 5 as a function of the internuclear distance (q) between two reactive carbons.…”

Section: Theoretical Studymentioning

confidence: 99%

Photochromism of diarylethene molecules and crystals

Irie

2010

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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100

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“…12−16 Previous theoretical works based on the exploration of the potential energy surface (PES) at the complete active space selfconsistent field (CASSCF) level 15,17−19 allowed rationalization of this outcome; the CF → OF pathway of the first excited state (S 1 ) includes a barrier in N-DTE but a more favorable downhill profile in I-DTE. 15 These theoretical studies also pointed out the existence of a conical intersection (CI) between S 0 and S 1 for N-DTE, involved in both cyclization and cycloreversion processes.…”

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confidence: 95%

Inverse versus Normal Dithienylethenes: Computational Investigation of the Photocyclization Reaction

Perrier

Aloïse

Olivucci

et al. 2013

J. Phys. Chem. Lett.

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The understanding of the intimate electronic processes in photochromes is essential to optimize the properties of light-controllable devices. For one of the most studied classes of molecular switches, namely, dithienylethenes, the relative efficiencies of the normal and inverse structures remained puzzling. Indeed, despite a larger ratio of the active antiparallel conformers for the latter, the quantum yields of cyclization of inverse dithienylethenes do not exceed those of its normal counterpart. In the present contribution, we provide the first explanation of this experimental outcome using multireference ab initio quantum chemistry. We demonstrate the existence of a fluorescent intermediate on the S 1 state of the inverse system that generates a photochemically unreactive conformation in the ground state. This study paves the way toward a rational development of efficient molecular photochromes presenting a photon-quantitative response.

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“…29 Ultimately, the desired switching efficiency can be achieved predictably only by unravelling the fundamental principles that determine the efficiency of the switching processes in these systems. To date, the majority of studies of switching efficiency have centered on theoretical investigations 30 and comparison of quantum yields of existing derivatives 31 and on geometrical optimizations of reacting atoms toward ring closing.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches

et al. 2013

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Diarylethene photochromic switches use light to drive structural changes through reversible electrocyclization reactions. High efficiency in dynamic photoswitching is a prerequisite for applications, as is thermal stability and the selective addressability of both isomers ring-opened and -closed diarylethenes. These properties can be optimized readily through rational variation in molecular structure. The efficiency with regard to switching as a function of structural variation is much less understood, with the exception of geometric requirements placed on the reacting atoms. Ultimately, increasing the quantum efficiency of photochemical switching in diarylethenes requires a detailed understanding of the excited-state potential energy surface(s) and the mechanisms involved in switching. Through studies of the temperature dependence, photoswitching and theoretical studies demonstrate the occurrence or absence of thermal activation barriers in three constitutional isomers that bear distinct π-conjugated systems. We found that a decrease in the thermal barriers correlates with an increase in switching efficiency. The origin of the barriers is assigned to the decrease in π-conjugation that is concomitant with the progress of the photoreaction. Furthermore, we show that balanced molecular design can minimize the change in the extent of π-conjugation during switching and lead to optimal bidirectional switching efficiencies. Our findings hold implications for future structural design of diarylethene photochromic switches.

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Quantum yields and potential energy surfaces: a theoretical study

Cited by 55 publications

References 23 publications

Photochromism of diarylethene molecules and crystals

Photochromism of diarylethene molecules and crystals

Inverse versus Normal Dithienylethenes: Computational Investigation of the Photocyclization Reaction

Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches

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