Precious and rare elements have traditionally dominated inorganic photophysics and photochemistry, but now we are witnessing a paradigm shift toward cheaper and more abundant metals. Even though emissive complexes based on selected first-row transition metals have long been known, recent conceptual breakthroughs revealed that a much broader range of elements in different oxidation states are useable for this purpose. Coordination compounds of V, Cr, Mn, Fe, Co, Ni, and Cu now show electronically excited states with unexpected reactivity and photoluminescence behavior. Aside from providing a compact survey of the recent conceptual key advances in this dynamic field, our Perspective identifies the main design strategies that enabled the discovery of fundamentally new types of 3d-metal-based luminophores and photosensitizers operating in solution at room temperature.

There is a long-standing interest in iron­(II) complexes that emit from metal-to-ligand charge transfer (MLCT) excited states, analogous to ruthenium­(II) polypyridines. The 3d6 electrons of iron­(II) are exposed to a relatively weak ligand field, rendering nonradiative relaxation of MLCT states via metal-centered excited states undesirably efficient. For isoelectronic chromium(0), chelating diisocyanide ligands recently provided access to very weak MLCT emission in solution at room temperature. Here, we present a concept that boosts the luminescence quantum yield of a chromium(0) isocyanide complex by nearly 2 orders of magnitude, accompanied by a significant increase of the MLCT lifetime. Pyrene units in the diisocyanide ligand backbone lead to an enlarged π-conjugation system and to a strongly delocalized MLCT state, from which nonradiative relaxation is less dominant despite a sizable redshift of the emission. While the pyrene moiety is electronically coupled to the core of the chromium(0) complex in the excited state, UV–vis absorption and 2D NMR spectroscopy show that this is not the case in the ground state. Luminescence lifetimes and quantum yields for our pyrenyl-decorated chromium(0) complex exhibit an unusual bell-shaped dependence on solvent polarity, indicative of two counteracting effects governing the MLCT deactivation. These two effects are identified as predominant deactivation either through an energetically nearby lying metal-centered state in the most apolar solvents, or alternatively via direct nonradiative relaxation to the ground state following the energy gap law in more polar solvents. This is the first example of a 3d6 MLCT emitter to benefit from an increased π-conjugation network.

The reactivity of [Fe (tpena)] (tpena=N,N,N'-tris(2-pyridylmethyl)ethylenediamine-N'-acetate) as a catalyst for oxidation reactions depends on its ratio to the terminal oxidant H O and presence or absence of sacrificial substrates. The outcome can be switched between: 1) catalysed H O disproportionation, 2) selective catalytic oxidation of methanol or benzyl alcohol to the corresponding aldehyde, or 3) oxidative decomposition of the tpena ligand. A common mechanism is proposed involving homolytic O-O cleavage in the detected transient purple low-spin (S=1/2 ) [(tpenaH)Fe O-OH] . The resultant iron(IV) oxo and hydroxyl radical both participate in controllable hydrogen-atom transfer (HAT) reactions. Consistent with the presence of a weaker σ-donor carboxylate ligand, the most pronounced difference in the spectroscopic properties of [Fe(OOH)(tpenaH)] and its conjugate base, [Fe(OO)(tpenaH)] , compared to non-heme iron(III) peroxide analogues supported by neutral multidentate N-only ligands, are slightly blue-shifted maxima of the visible absorption band assigned to ligand-to-metal charge-transfer (LMCT) transitions and, corroborating this, lower Fe /Fe redox potentials for the pro-catalysts.

Coordination complexes of precious metals with the d6 valence electron configuration such as Ru(II), Os(II) and Ir(III) are used for lighting applications, solar energy conversion and photocatalysis. Until now, d6 complexes made from abundant first-row transition metals with competitive photophysical and photochemical properties have been elusive. While previous research efforts focused mostly on Fe(II), we disclose that isoelectronic Cr(0) gives access to higher photoluminescence quantum yields and excited-state lifetimes when compared with any other first-row d6 metal complex reported so far. The luminescence behaviour of the metal-to-ligand charge transfer excited states of these Cr(0) complexes is competitive with Os(II) polypyridines. With these Cr(0) complexes, the metal-to-ligand charge transfer states of first-row d6 metal complexes become exploitable in photoredox catalysis, and benchmark chemical reductions proceed efficiently under low-energy red illumination. Here we demonstrate that appropriate molecular design strategies open up new perspectives for photophysics and photochemistry with abundant first-row d6 metals.

Many organometallic iridium(III) complexes have photoactive excited states with mixed metal-to-ligand and intraligand charge transfer (MLCT/ILCT) character, which form the basis for numerous applications in photophysics and photochemistry. Cobalt(III) complexes with analogous MLCT excited-state properties seem to be unknown yet, despite the fact that iridium(III) and cobalt(III) can adopt identical low-spin d 6 valence electron configurations due to their close chemical relationship. Using a rigid tridentate chelate ligand (L CNC ), in which a central amido π-donor is flanked by two σ-donating N-heterocyclic carbene subunits, we obtained a robust homoleptic complex [Co(L CNC ) 2 ](PF 6 ), featuring a photoactive excited state with substantial MLCT character. Compared to the vast majority of isoelectronic iron(II) complexes, the MLCT state of [Co(L CNC ) 2 ](PF 6 ) is long-lived because it does not deactivate as efficiently into lower-lying metal-centered excited states; furthermore, it engages directly in photoinduced electron transfer reactions. The comparison with [Fe(L CNC ) 2 ](PF 6 ), as well as structural, electrochemical, and UV–vis transient absorption studies, provides insight into new ligand design principles for first-row transition-metal complexes with photophysical and photochemical properties reminiscent of those known from the platinum group metals.