Litcius/Paper detail

A Photoreactive Iron(II) Complex Luminophore

Wolfgang Leis, Miguel A. Argüello Cordero, Stefan Lochbrunner, Hartmut Schubert, Andreas Berkefeld

2022Journal of the American Chemical Society113 citationsDOI

Abstract

Controlling the order and lifetimes of electronically excited states is essential to effective light-to-potential energy conversion by molecular chromophores. This work reports a luminescent and photoreactive iron(II) complex, the first performant group homologue of prototypical sensitizers of ruthenium. Double cyclometalation of a phenylphenanthroline framework at iron(II) favors the population of a triplet metal-to-ligand charge transfer (3MLCT) state as the lowest energy excited state. Near-infrared (NIR) luminescence exhibits a monoexponential decay with τ = 2.4 ns in the solid state and 1 ns in liquid phase. Lifetimes of 14 ns at 77 K are in line with a narrowing of the NIR emission band at λem,max = 1170–1230 nm. Featuring a 3MLCT excited-state redox potential of −2 V vs the ferrocene/ferrocenium couple, the use of the Fe(II) chromophore as a sensitizer for light-driven synthesis is exemplified by the radical cross-coupling of 4-chlorobromobenzene and benzene.

Topics & Concepts

ChemistryLuminophoreExcited stateChromophoreLuminescencePhotochemistryFerroceneRutheniumPopulationPhysical chemistryAtomic physicsElectrochemistryOptoelectronicsElectrodeOrganic chemistrySociologyPhysicsCatalysisDemographyRadical Photochemical ReactionsPhotochemistry and Electron Transfer StudiesOxidative Organic Chemistry Reactions