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Luminescence and reactivity of a charge-transfer excited iron complex with nanosecond lifetime

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Science  18 Jan 2019:
Vol. 363, Issue 6424, pp. 249-253
DOI: 10.1126/science.aau7160

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Orange-glowing iron at room temperature

Many photoactive coordination compounds contain precious metals. Replacing ruthenium with more–earth-abundant iron has been a long-sought goal, but iron compounds generally relax too rapidly after light absorption to channel the energy productively. Kjær et al. prepared an iron compound with an excited state stable enough to emit light for nanoseconds, or that could engage in bimolecular electron transfer (see the Perspective by Young and Oldacre). Targeting a ligand-to-metal rather than metal-to-ligand charge-transfer state was key to the achievement, as was the octahedral coordination environment rigidly enforced by two tridentate carbene ligands.

Science, this issue p. 249; see also p. 225

Abstract

Iron’s abundance and rich coordination chemistry are potentially appealing features for photochemical applications. However, the photoexcitable charge-transfer states of most iron complexes are limited by picosecond or subpicosecond deactivation through low-lying metal-centered states, resulting in inefficient electron-transfer reactivity and complete lack of photoluminescence. In this study, we show that octahedral coordination of iron(III) by two mono-anionic facial tris-carbene ligands can markedly suppress such deactivation. The resulting complex [Fe(phtmeimb)2]+, where phtmeimb is {phenyl[tris(3-methylimidazol-1-ylidene)]borate}, exhibits strong, visible, room temperature photoluminescence with a 2.0-nanosecond lifetime and 2% quantum yield via spin-allowed transition from a doublet ligand-to-metal charge-transfer (2LMCT) state to the doublet ground state. Reductive and oxidative electron-transfer reactions were observed for the 2LMCT state of [Fe(phtmeimb)2]+ in bimolecular quenching studies with methylviologen and diphenylamine.

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