A Tetracarbene Iron(II) Complex with a Long‐lived Triplet Metal‐to‐ligand Charge Transfer State due to a Triplet‐Triplet Barrier

Abstract

Mixed N‐heterocyclic carbene (NHC) / pyridyl iron(II) complexes have attracted a great deal of attention recently because of their potential as photocatalysts and light sensitizers made from Earth‐abundant elements. The most decisive challenge for their successful implementation is the lifetime of the lowest triplet metal‐to‐ligand charge transfer state (3MLCT), which typically decays via a triplet metal‐centered (3MC) state back to the ground state. We reveal by variable‐temperature ultrafast transient absorption spectroscopy that the tripodal iron(II) bis(pyridine) complex isomers trans‐ and cis‐[Fe(pdmi)2]2+with four NHC donors show 3MLCT→3MC population transfers with very different barriers and rationalize this by computational means. While trans‐[Fe(pdmi)2]2+possesses an unobservable activation barrier, the cis isomer exhibits a barrier of 492 cm–1, which leads to a nanosecond 3MLCT lifetime at 77 K. The kinetic and quantum chemical data were analyzed in the context of semi‐classical Marcus theory revealing a high reorganization energy and small electronic coupling between the two triplet states. This highlights the importance of detailed structural control and kinetic knowledge for the rational design of photosensitizers from first row transition metals such as iron.