Probing the photoexcited states of rhodium corroies by time-resolved Q-band EPR. Observation of strong spin-orbit coupling effects

The photoexcited states of two 5,10,15-tris(pentafluorophenyl)corroles (tpfc), hosting Rh(III) in their core, namely Rh(pyr)(PPh₃)(tpfc) and Rh(PPh₃)(tpfc), have been studied by time-resolved electron paramagnetic resonance (TREPR) combined with pulsed laser excitation. Using the transient nutation technique, the spin polarized spectra are assigned to photoexcited triplet states. The spectral widths observed for the two Rh(III) corroles crucially depend on the axial ligands at the Rh(III) metal ion. In case of Rh(PPh3)(tpfc), the TREPR spectra are found to extend over 200 mT, which exceeds the spectral width of non-transition-metal corroles by more than a factor of 3. Moreover, the EPR lines of the Rh(III) corroles are less symmetric than those of the non-transition-metal corrroles. The peculiarities in the TREPR spectra of the Rh(III) corroles can be rationalized in terms of strong spin-orbit coupling (SOC) associated with the transition-metal character of the Rh(III) ion. It is assumed that SOC in the photoexcited Rh(III) corroles effectively admixes metal centered ³dd-states to the corrole centered ³ππ*-states detected in the TREPR experiments. This admixture leads to an increased zero-field splitting and a large g-tensor anisotropy as manifested by the excited Rh(III) corroles.