Ferrous and ferric complexes with cyclometalating N-heterocyclic carbene ligands: a case of dual emission revisited

Iron N-heterocyclic carbene (FeNHC) complexes with long-lived charge transfer states are emerging as a promising class of photoactive materials. We have synthesized [Fe(II)(ImP)(2)] (ImP = bis(2,6-bis(3-methylimidazol-2-ylidene-1-yl)phenylene)) that combines carbene ligands with cyclometalation for additionally improved ligand field strength. The 9 ps lifetime of its (3)MLCT (metal-to-ligand charge transfer) state however reveals no benefit from cyclometalation compared to Fe(ii) complexes with NHC/pyridine or pure NHC ligand sets. In acetonitrile solution, the Fe(ii) complex forms a photoproduct that features emission characteristics (450 nm, 5.1 ns) that were previously attributed to a higher ((2)MLCT) state of its Fe(iii) analogue [Fe(III)(ImP)(2)](+), which led to a claim of dual (MLCT and LMCT) emission. Revisiting the photophysics of [Fe(III)(ImP)(2)](+), we confirmed however that higher ((2)MLCT) states of [Fe(III)(ImP)(2)](+) are short-lived (<10 ps) and therefore, in contrast to the previous interpretation, cannot give rise to emission on the nanosecond timescale. Accordingly, pristine [Fe(III)(ImP)(2)](+) prepared by us only shows red emission from its lower (2)LMCT state (740 nm, 240 ps). The long-lived, higher energy emission previously reported for [Fe(III)(ImP)(2)](+) is instead attributed to an impurity, most probably a photoproduct of the Fe(ii) precursor. The previously reported emission quenching on the nanosecond time scale hence does not support any excited state reactivity of [Fe(III)(ImP)(2)](+) itself.