The Cr^III-polypyridyl complexes are appealing for their long-lived near-infrared (NIR) emission

reaching the millisecond range and for the strong circularly polarized luminescence (CPL) 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 non-symmetrical Cr^III-dyads

exhibiting directional intramolecular intermetallic energy transfers remain unexplored. Taking

advantage of the inertness of heteroleptic Cr^III-polypyridyl building blocks, we herein adapt the

‘complex-as-ligand’ strategy, largely used with precious 4d and 5d metals, for preparing a binuclear

non-symmetrical Cr^III complex (3d metal). The resulting [(phen)2Cr(L)Cr(tpy)]⁶⁺ dyad shows double

long-lived NIR emission and a directional intermetallic energy transfer which 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.