Improving photosensitivity without changing thermal reactivity in photochromic diarylbenzenes based on accurate prediction by DFT calculations.

1,2-Diarylbenzenes (DABs) have been developed as a new family of fast T-type photochromic switches. However, the molecular design strategy for DABs with desired optical and thermal properties is not established. In this work, we explored the best functional in quantum chemical calculations to predict the properties of DABs. Furthermore, we newly designed and synthesized DABs based on the calculation using the best functional, resulting in the improvement of the photosensitivity in the UV-A region (i.e. a shift of absorption to lower energies and an increase in the absorption coefficient) without changing the thermal back-reaction rate.

Cyclization reaction dynamics of an inverse type diarylethene derivative as revealed by time-resolved absorption and fluorescence spectroscopies.

Photocyclization reaction dynamics of an inverse type diarylethene derivative was investigated in alkane solutions by means of ultrafast laser spectroscopies. Femtosecond transient absorption spectroscopy showed that the Franck-Condon state formed by photoexcitation is geometrically relaxed to a transient species within 100 fs and subsequently the cyclization process takes place with a time constant of 36 ps. This time constant is much longer than those in normal type derivatives. Steady-state and time-resolved fluorescence measurements with the aid of quantum chemical calculations revealed that there exist three kinds of conformers, one parallel and two anti-parallel forms, in the ground state. One of the anti-parallel conformers undergoes the cyclization reaction, while the other two conformers are nonreactive species and their major relaxation processes are radiative decay and intersystem crossing into the triplet states. The triplet states thus formed no longer undergo the cyclization reaction in the late time region.

Optical properties and solvatofluorochromism of fluorene derivatives bearing S,S-dioxidized thiophene.

We synthesized fluorene derivatives having phenylthiophene (FPT) or benzothiophene (FBT), and their S,S-dioxidized compounds (FPTO2, FPTO4, FBTO2 and FBTO4), which are prepared by oxidation of the thiophene rings in FPT and FBT with m-chloroperoxybenzoic acid. FPT and FBT exhibited similar optical properties for absorption maximum wavelength, fluorescence maximum wavelength and fluorescence quantum yield. However, the absorption and fluorescence spectra of FPTO2 were largely shifted toward a longer wavelength in comparison with those of FPT, and their fluorescence quantum yields dramatically decreased with oxidation. In contrast, the absorption and fluorescence spectra and the fluorescence quantum yields of FBTO2 and FBTO4 were similar to those of FBT. Moreover, FPTO2 and FBTO2 showed strong solvatofluorochromism. Such solvent dependent properties are ascribed to the charge transfer character of the molecule.

Fluorescence On/Off Switching in Nanoparticles Consisting of Two Types of Diarylethenes.

Single- and double-component nanoparticles consisting of two types of diarylethenes, 1,2-bis(3-methyl-5-phenyl-2-thienyl)perfluorocyclopentene (1a) and 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (2a), were fabricated by a reprecipitation method. Nanoparticles consisting of 1a exhibited orange or green fluorescence depending on the fabrication condition and did not undergo any photocyclization reaction. On the other hand, nanoparticles consisting of 2a underwent photoreversible photochromic reactions upon alternating irradiation with ultraviolet and visible light. Nanoparticles consisting of 1a and 2a exhibited fluorescence on/off switching with rapid switching speed and high on/off contrast, accompanying the photochromic reactions of 2a. The dependence of fluorescence on/off switching properties on Förster distance and molar fraction was observed and quantitatively evaluated by a simplified model.