Hetero‐bimetallic Lanthanide‐Coinage Metal Compounds Featuring Possible Metal‐Metal Interactions in the Excited State

Heterometallic complexes, combining metals of the outer rims of the d‐block, for example lanthanides(III) (Ln) and coinage metals(I) (M) are scarcely reported, synthetically challenging and highly interesting in terms of their interactions. In this context, we synthesized hetero‐bimetallic Ln−M compounds ligated by the phosphine functionalized amidinate system (N,N’‐bis[(2‐diphenylphosphino)phenyl]formamidinate, “dpfam”). The resulting compounds [dpfam(3)LnM][OTf] (Ln = La, Nd and M = Ag, Au) feature a close proximity of the two metal centres and were investigated experimentally by photoluminescence spectroscopy and quantum chemical calculations. The latter showed rare La−Au interactions for the first excited state.