Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene derivative

Abstract

Abstract Near-infrared two-photon absorption and excited state dynamics of a fluorescent diarylethene (fDAE) derivative were investigated by time-resolved absorption and fluorescence spectroscopies. Prescreening with quantum chemical calculation predicted that a derivative with methylthienyl groups (mt-fDAE) in the closed-ring isomer has a two-photon absorption cross-section larger than 1000 GM, which was experimentally verified by Z-scan measurements and excitation power dependence in transient absorption. Comparison of transient absorption spectra under one-photon and simultaneous two-photon excitation conditions revealed that the closed-ring isomer of mt-fDAE populated into higher excited states deactivates following three pathways on a timescale of ca. 200 fs: (i) the cycloreversion reaction more efficient than that by the one-photon process, (ii) internal conversion into the S 1 state, and (iii) relaxation into a lower state (S 1 ’ state) different from the S 1 state. Time-resolved fluorescence measurements demonstrated that this S 1 ’ state is relaxed to the S 1 state with the large emission probability. These findings obtained in the present work contribute to extension of the ON–OFF switching capability of fDAE to the biological window and application to super-resolution fluorescence imaging in a two-photon manner. Graphical Abstract