Thirteen neutral complexes [ExMyXz-(PPh3)(n)(L)(m)] (E = Bi, Sb; M = Cu, Ag; X = Cl, Br, I; L = solvent) featuring three different motifs were prepared and characterized regarding their structure, stability, and absorption spectra. While not identical in structural motif, the compounds can serve as models for the influence of the composition E/M/X on the optical properties of double perovskites A(2)EMX(6) (A = Cs, CH3NH3).