Carbon–sulfur bond elongation as the promoting reaction coordinate in the efficient sub-nanosecond intersystem crossing in thianaphthene derivatives

Abstract

Thiophene derivatives have become integral to OLEDs, photovoltaics, and photodynamic therapy research. A deeper understanding of their excited state dynamics and electronic relaxation mechanisms is expected to provide important physical insights of direct relevance for these applications. In this study, thianaphthene (TN), 2-methylbenzothiophene (2MBT), and 3-methylbenzothiophene (3MBT) are investigated using femtosecond broadband transient absorption and steady-state spectroscopy techniques along with time-dependent density functional calculations in cyclohexane and acetonitrile. The photophysical properties and electronic relaxation mechanisms of these derivatives are elucidated. Small fluorescence quantum yields ranging from 0.4 to 1.1% are measured. It is demonstrated that excitation of TN at 290 nm leads primarily to intersystem crossing to the triplet manifold with a lifetime of 400 ± 15 ps in either solvent, whereas four- to twofold shorter intersystem crossing lifetimes are measured for 2MBT and 3MBT depending on whether cyclohexane or acetonitrile is used. Linear interpolation of internal coordinates evidence that elongation of the S–C bonds enables ultrafast intersystem crossing in these thiophene derivatives involving singlet and triplet states with ππ* and πσ* characters. Excitation at 266 nm results in an additional 5 ± 1 ps lifetime, which is assigned to intramolecular vibrational relaxation dynamics occurring in the excited singlet state.