Photochromic Diarylethenes with Heterocyclic Aromatic Rings: Correlation between Thermal Bistability and Geometrical Characters of Transition States

Li, Xin; Zou, Qi; Ågren, Hans

doi:10.1021/acs.jpca.5b04268

Cited by 14 publications

(8 citation statements)

References 63 publications

(113 reference statements)

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“…DFT and TD-DFT calculations were performed with the Gaussian09 package . We worked at the ωB97xD 6-31G(d,p) level of theory, since it is known to give accurate descriptions of DAE derivatives while taking into account dispersion forces . Moreover, to model the bulk THF solvent effect on DFT, TD-DFT, and transient state calculations, we used the cost-effective PCM model.…”

Section: Resultsmentioning

confidence: 97%

Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources

et al. 2016

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In this paper, we present a novel concept for "smarter" photolabile organic compounds combining not one but two caged functions. As proof of principle, this diarylethene-based compound possesses two inhibited chemical groups (OMe and OAc) and its efficient release in different solvents is reported. In low- to medium-polarity media, both MeOH and AcOH are released, with a slight preferential uncaging of AcOH except in 1,4-dioxane, where MeOH is preferentially released. In contrast, DMSO or DMF render AcOH release strongly dominating. DFT calculations of the corresponding photoreactive conformations not only afford strong support to the observed release of MeOH and AcOH but also qualitatively explain the preferential release of acid in terms of dispersive noncovalent interactions. Finally, mechanistic aspects are discussed on the bases of the spectroscopic observations and of the TD-DFT calculations.

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Section: Resultsmentioning

confidence: 97%

Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources

et al. 2016

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“…To evaluate the geometry in the transition state, the distance between the reacting carbon atoms and torsion angle of the methyl group on the reacting carbon atom relative to the thiophene ring were calculated (Table S6). Figure shows the relationship of these parameters relative to E a ; the average value of two torsion angles was used. As can be seen, the absolute value of both the parameters increased with increasing E a .…”

Section: Resultsmentioning

confidence: 99%

Tuning of Optical Properties and Thermal Cycloreversion Reactivity of Photochromic Diarylbenzene by Introducing Electron-Donating Substituents

2019

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Thermally reversible photochromic compounds having excellent physicochemical properties can be exploited for many practical applications, such as ophthalmic lenses, real-time holography, and super-resolution microscopy. In this study, we have designed and synthesized novel 1,2diarylbenzene derivatives bearing various electron-donating substituents at p-position of the 2 phenyl ring to tune the optical and thermal properties for the practical applications. Introduction of the electron-donating groups resulted in the red-shift of the absorption spectra, increase in the absorption coefficients of the open-ring isomers, and deceleration of the thermal cycloreversion of the closed-ring isomers. Theoretical analysis based on Hammett's substituent constant and density functional theory revealed that the rate of thermal cycloreversion became lower in proportion to the electron-donating ability of the substituent. The novel 1,2-diarylbenzene derivatives synthesized here could undergo photocyclization upon irradiation with UV-A light and fast thermal cycloreversion with a half-life of a few hundred milliseconds to seconds.

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“…We performed thermodynamic calculations at the ωB97xD/6-31G(d,p) level of theory. This method provide acceptable results for thermochemistry, and it was used previously for theoretical insight into diarylethene transformations. , According to these calculations, the first stages of three proposed pathways ([1,9]-H shift, deprotonation, protonation) are thermodynamically favorable in the gas phase (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties

et al. 2018

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Photoinduced rearrangement of diarylethenes to naphthalenes or isoelectronic benzoannulated heterocycles is a novel reaction in preparative organic photochemistry. Recently it was shown that unsymmetrical diarylethenes containing benzene and oxazole derivatives efficiently undergo this transformation leading to amide derivatives of naphthalene. Mechanistic study of skeletal rearrangement for a typical representative of these compounds, namely 3-(5-methyl-2-phenyl-1,3-oxazol-4-yl)-2-phenylcyclopent-2-en-1-one, was performed by stationary and laser flash photolysis as well as density functional theory (DFT) calculations. The mechanism of the rearrangement was found to comprise several thermal stages. Both singlet and triplet states of the initial compound can be transformed to the reaction product, which results in the dependence of the quantum yield vs concentration of dissolved oxygen. Three reactive intermediates were registered in the laser flash photolysis experiment; the predicted structures were in accordance with DFT calculations of the electronic absorption spectra. In addition to the previously proposed mechanism of skeletal rearrangement based on a sigmatropic shift of hydrogen, two new parallel pathways based on formation of a carbanion/carbocation were determined.

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Photochromic Diarylethenes with Heterocyclic Aromatic Rings: Correlation between Thermal Bistability and Geometrical Characters of Transition States

Cited by 14 publications

References 63 publications

Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources

Dual Photochemical Bond Cleavage for a Diarylethene-Based Phototrigger Containing both Methanolic and Acetic Sources

Tuning of Optical Properties and Thermal Cycloreversion Reactivity of Photochromic Diarylbenzene by Introducing Electron-Donating Substituents

Mechanistic Aspects of Photoinduced Rearrangement of 2,3-Diarylcyclopentenone Bearing Benzene and Oxazole Moieties

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