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

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.