Nanosecond laser flash photolysis of a 6-nitroindolinospiropyran in solution and in nanocrystalline suspension under single excitation conditions

Abstract

Nanosecond transient absorption spectroscopy was used to study the photochemical ring-opening reaction for a 6-nitroindolinospiropyran (SP1) in solution and in nanocrystalline (NC) suspension at 298 K. We measured the kinetics in argon purged and air saturated acetonitrile and found that the presence of oxygen affected two out of the three components of the kinetic decay at 440 nm. These are assigned to the triplet excited states of the Z- and E-merocyanines (³Z-MC* and ³E-MC*). In contrast, a long-lived growth component at 550 nm and the decay of a band centered at 590 nm showed no dependence on oxygen and are assigned, respectively, to the ground state Z- and E-merocyanines (Z-MC₀ and E-MC₀). Laser flash photolysis studies performed in NC suspensions initially showed a very broad, featureless absorption spectrum that decayed uniformly for ca. 70 ns before revealing a more defined spectrum that persisted for greater than 4 ms and is consistent with a mixture of the more stable Z- and E-MC₀ structures. We performed quantum mechanical calculations on the interconversion of E- and Z-MCs on the S₀ and S₁ potential energy surfaces. The computed UV-vis spectra for a scan along the Z → E interconversion reaction coordinate show substantial absorptivity from 300–600 nm, which suggests that the broad, featureless transient absorption spectrum results from the contribution of the transition structure and other high-energy species during the Z to E isomerization.