In molecular photochemistry, charge-transfer emission is well understood and widely exploited. In contrast, luminescent metal-centered transitions only came into focus in recent years. This gave rise to strongly phosphorescent CrIII complexes with a d3 electronic configuration featuring luminescent metal-centered excited states which are characterized by the flip of a single spin. These so-called spin-flip emitters possess unique properties and require different design strategies than traditional charge-transfer phosphors. In this review, we give a brief introduction to ligand field theory as a framework to understand this phenomenon and outline prerequisites for efficient spin-flip emission including ligand field strength, symmetry, intersystem crossing and common deactivation pathways using CrIII complexes as instructive examples. The recent progress and associated challenges of tuning the energies of emissive excited states and of emerging applications of the unique photophysical properties of spin-flip emitters are discussed. Finally, we summarize the current state-of-the-art and challenges of spin-flip emitters beyond CrIII with d2, d3, d4 and d8 electronic configuration, where we mainly cover pseudooctahedral molecular complexes of V, Mo, W, Mn, Re and Ni, and highlight possible future research opportunities.
Keywords: Excited states; Intersystem crossing; Ligand field theory; Photochemistry; Spin-flip phosphorescence; Transition metal complex.
© 2022. The Author(s).