4.4 Article

Excitation wavelength- and intensity-dependent stepwise two-photon-induced photochromic reaction

Journal

PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES
Volume 21, Issue 8, Pages 1445-1458

Publisher

SPRINGERNATURE
DOI: 10.1007/s43630-022-00234-y

Keywords

Photochromism; Two-photon absorption; Non-linear optical response; Imidazole dimer; Biradical

Funding

  1. JSPS KAKENHI [JP18H05263]

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In recent years, photochromic molecules with wavelength-selective or light intensity-dependent photoresponses have gained increasing attention. This study presents the design of stepwise two-photon induced photochromic molecules (PABI-PIC and PABI-PIC2) consisting of two different photochromic units. The stepwise photochromic properties of these molecules can be easily controlled depending on the excitation light intensity and wavelength. These molecular designs are important for the development of advanced photoresponsive materials.
The photochromic molecules showing wavelength-selective or light intensity-dependent photoresponse are receiving increased attention in recent years. Although a photoswitch with a single chromophore can control the ON and OFF states of a function, that consisting of multi-chromophores would be useful for the specific control in complex systems. Herein, we designed stepwise two-photon induced photochromic molecules (PABI-PIC and PABI-PIC2) consisting of two different photochromic units (PABI and PIC). One-photon absorption reaction in the UV light region of PABI-PIC generates the short-lived transient biradical (BR) that absorbs an additional photon in the visible and UV light region in a stepwise manner to produce the two-photon photochemical product, the quinoidal species (Quinoid). The photochromic properties of these transient species are completely different in color and fading speed. In addition, PABI-PIC also shows the excitation wavelength-dependent photochromism because the excited states of the PABI and PIC units are electronically orthogonal. Therefore, the stepwise photochromic properties of PABI-PIC are easily controlled depending on the excitation light intensity and wavelength. These molecular designs are important for the development of advanced photoresponsive materials. [GRAPHICS] .

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