Ultrafast Time-Resolved Spectroscopy of Diarylethene-Based Photoswitchable Deoxyuridine Nucleosides

Photoswitches based on the diarylethene architecture have been attracting considerable attention for the investigation and control of a variety of biological processes. The reversible photoisomerization reaction between their open- and closed-ring forms can be selectively addressed by irradiation with light of two markedly different wavelengths. In this work, the dynamics of the photochromic ring-opening reaction of four novel diarylethene-based photoswitchable deoxyuridine nucleosides is investigated by femtosecond transient absorption. Upon photoexcitation with sub-20 fs pulses in the first absorption band (500 nm), all four photoswitches showed a fast ballistic excited-state deactivation within less than 500 fs toward the S1/S0 conical intersection. Transient data was globally analyzed, and a relaxation kinetic model with a branching between open and closed ring forms without any loss channels was derived. Ring-opening quantum yields, Φr-o, were found to strongly depend on the substituents (R), ranging from 0.64 (dU(PSI): R = 2-naphthyl) to 0.30 (dU(PSIV): R = 2-pyridyl).