Energy- and conformer-dependent excited-state relaxation of an E/Z photoswitchable thienyl-ethene

Abstract

Bis(bithienyl)-1,2-dicyanoethene (4TCE) is a photoswitch that operates via reversible E/Z photoisomerization following absorption of visible light. cis-to-trans photoisomerization of 4TCE requires excitation below 470 nm, is relatively inefficient (quantum yield < 5%) and occurs via the lowest-lying triplet. We present excitation-wavelength dependent (565–420 nm) transient absorption (TA) studies to probe the photophysics of cis-to-trans isomerization to identify sources of switching inefficiency. TA data reveals contributions from more than one switch conformer and relaxation cascades between multiple states. Fast (∼4 ps) and slow (∼40 ps) components of spectral dynamics observed at low excitation energies (>470 nm) are readily attributed to deactivation of two conformers; this assignment is supported by computed thermal populations and absorption strengths of two molecular geometries (P_A and P_B) characterized by roughly parallel dipoles for the thiophenes on opposite sides of the ethene bond. Only the P_B conformer is found to contribute to triplet population and the switching of cis-4TCE: high-energy excitation (<470 nm) of P_B involves direct excitation to S₂, relaxation from which prepares an ISC-active S₁ geometry (ISC QY 0.4–0.67, k_ISC ∼ 1.6–2.6 × 10⁻⁹ s⁻¹) that is the gateway to triplet population and isomerization. We ascribe low cis-to-trans isomerization yield to excitation of the nonreactive P_A conformer (75–85% loss) as well as loses along the P_B S₂ → S₁ → T₁ cascade (10–20% loss). In contrast, electrocyclization is inhibited by the electronic character of the excited states, as well as a non-existent thermal population of a reactive “antiparallel” ring conformation.