Ultrafast photophysics of para-substituted 2,5-bis(arylethynyl) rhodacyclopentadienes: thermally activated intersystem crossing

Abstract

2,5-Bis(phenylethynyl) rhodacyclopentadienes (RCPDs), as a type of Rh(III) complex, exhibit unusually intense fluorescence and slow intersystem crossing (ISC) due to weak metal–ligand interactions. However, details on their ultrafast photophysics and ISC dynamics are limited. In this work, electronic relaxation upon photoexcitation of two substituted RCPDs with two –CO₂Me (A-RC-A) or –NMe₂/–CO₂Me (D-RC-A) end groups are comprehensively investigated using femtosecond transient absorption spectroscopy and theoretical analysis. Upon ultraviolet and visible excitation, dephasing of vibrational coherence, charge transfer, conformation relaxation, and ISC are observed experimentally. By calculating the spin–orbit coupling, reorganization energy, and adiabatic energy gap of plausible ISC channels, semi-classical Marcus theory revealed the dominance of thermally activated ISC (S₁ → T₂) for both D-RC-A and A-RC-A, while S₁ → T₁ channels are largely blocked due to high ISC barriers. With weak spin–orbit coupling, such differences in plausible ISC channels are predominately tuned by energetic parameters. Singlet oxygen sensitization studies of A-RC-A provide additional insight into the excited-state behavior of this complex.