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 [dpfam3LnM][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
