Transient absorption spectroscopy on spiropyran monolayers using nanosecond pump–probe Brewster angle reflectometry

Abstract

Self-assembled monolayers of 11-(3′,3′-dimethyl-6,8-dinitrospiro[chromene-2,2′-indoline]-1′-yl) undecanoic acid (amphiphilic spiropyran) at the air–water interface are studied using Brewster angle reflectometry. Transient kinetics of the spiropyran to merocyanine conversion are recorded in a UV-pump, VIS-probe configuration. By varying the probe wavelength using an optical parametric oscillator, we are able to reconstruct absorption spectra of intermediate states with a time-resolution of 10 nanoseconds, limited by the temporal convolution of the two laser pulses. After UV irradiation, spiropyran converts to merocyanine in two stages. The first occurs within a timescale of several tens of nanoseconds and is heavily convoluted with the system response time, whereas the second stage occurs over a few hundred nanoseconds. During the rise time there is a small red shift in the transient absorption spectrum of ∼20 nm. We assign the red shift and the slower kinetics to the isomerization of a merocyanine isomer cis about the central methine bond to those that are trans about the same bond.