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 Cr^III 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 Cr^III 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 Cr^III 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.

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