Complex-as-Ligand Strategy as a Tool for the Design of a Binuclear Nonsymmetrical Chromium(III) Assembly: Near-Infrared Double Emission and Intramolecular Energy Transfer.

The chromium(III) polypyridyl complexes are appealing for their long-lived near-infrared (NIR) emission reaching the millisecond range and for the strong circularly polarized luminescence of their isolated enantiomers. However, harnessing those properties in functional polynuclear Cr III devices remains mainly inaccessible because of the lack of synthetic methods for their design and functionalization. Even the preparation and investigation of most basic nonsymmetrical Cr III dyads exhibiting directional intramolecular intermetallic energy transfer remain unexplored. Taking advantage of the inertness of heteroleptic chromium(III) polypyridyl building blocks, we herein adapt the "complex-as-ligand" strategy, largely used with precious 4d and 5d metals, for the preparation of a binuclear nonsymmetrical Cr III complex (3d metal). The resulting [(phen) 2 Cr( L )Cr(tpy)] 6+ dyad shows dual long-lived NIR emission and a directional intermetallic energy transfer that is controlled by the specific arrangements of the different coordination spheres. This strategy opens a route for building predetermined polynuclear assemblies with this earth-abundant metal.