Reaction dynamics of photochromic dithienylethene derivatives

Abstract The reaction dynamics of the photochromic ring-opening reaction of 1,2-bis(5-formyl-2-methyl-thien-3-yl)perfluorocyclopentene (CHO-BMTFP) in dichloromethane solution was investigated using femtosecond transient absorption spectroscopy. The data were analyzed in terms of a model potential and single-electron density matrices, which were calculated using the collective electronic oscillator (CEO) approach and the INDO/S semiempirical Hamiltonian. The S 0 –S 1 and S 0 –S 2 transitions of the closed isomer were resonantly excited using 120 fs pump pulses at 610 and 410 nm, respectively. A temporally delayed white light continuum probe pulse monitors the decay of the S 1 or S 2 state as well as the recovery of the S 0 state. Within the first picosecond after excitation, CHO-BMTFP was observed to undergo a fast structural relaxation along the S 1 potential energy surface into a minimum constituting a precursor of the ring-opening process. The rather long lifetime of the precursor, τ 2 =13 ps, was consistent with the calculated potential barrier in front of the conical intersection with the S 0 potential energy surface, which may arise from stabilization of the nearly planar closed isomer by an efficiently delocalized π-electron system.