Complexes [Pt(C₆F₅)(bzq)(CNR)] {R = ^tBu (1), 2-naphthyl (2), 2,6-Me₂Ph (3)} have been prepared by replacement of the labile acetone in [Pt(C₆F₅)(bzq)(Me₂CO)] with the corresponding isocyanide ligand. The structures 1 and 3 (X-ray) confirms their square planar geometry, with the bzq ligand coplanar to the metal plane. The reactions of 1-3 toward AgClO₄ lead to the trinuclear complexes [{Pt(C₆F₅)(bzq)(CNR)}₂Ag]ClO4 {R = tBu (4), 2-naphthyl (5)} or the tetranuclear [{Pt(C₆F₅)(bzq)(CN-2,6-Me₂Ph)Ag}₂](ClO₄)₂ (6). The structures of these three polynuclear complexes have been established by X-ray diffraction studies. Two pseudo-polymorphs of 4 (4a and 4b), only differing in the crystallization solvent, have been found. 4a/b and 5 are trinuclear Pt-Ag-Pt complexes with a "sandwich" disposition. In all three cases, two "Pt(C₆F₅)(bzq)(CNR)" fragments are linked by a silver atom through Pt → Ag bonds of donor acceptor nature and the silver center establishes a short η¹ interaction with the C_ipso of the bzq ligands. Furthermore, the study of the structure of 6 reveals two "(C₆F₅)(bzq)(CN-2,6-Me₂Ph)PtAg" subunits, each containing a Pt → Ag bond related by an inversion center and held together through η² interactions established by the silver atom of one unit and one of the aromatic rings of the bzq ligand of the other. The reaction of 1-3 with [Ag(OClO₃)(PPh₃)] produces [(C₆F₅)(bzq)(CNR)PtAg(PPh₃)]ClO₄ {R = ^tBu, (7), 2-naphthyl (7), 2,6-Me₂Ph (7)}. These dinuclear clusters contain a Pt → Ag bond and show dynamic processes in solution (NMR) which involve the rupture and formation of these interactions. The X-ray structure of 7 confirms the presence of a Pt-Ag bond and a η¹ interaction with the C_ipso of the bzq ligand (2.514(6) Å). All the crystal structures determined show π^...π interactions of the bzq which stack in a parallel fashion with interplanar distances of ca. 3.3-3.4 Å. In 5 and 6 the aromatic fragments of the isocyanide ligands also take part in these π^...π interactions. Absorption and emission properties of all the complexes 1-9 have been studied and explained with the aid of TD-DFT theoretical calculations. Compounds 1-9 are not emissive in solution but they are in rigid matrix. In glassy 2-Me-THF or CH₂Cl₂ at 77 K the Pt/Ag compounds 4-9 at any concentration (10^-3 M, 10^-4 M, 10^-5 M) show the same emission spectra as their corresponding starting complexes 1-3, in line with the rupture of the Pt-Ag bonds. In the solid state only the dinuclear compounds [Pt(C₆F₅)(bzq)(CN-^tBu)AgPPh₃)]ClO₄ (7) and [Pt(C₆F₅)(bzq)(CN-2,6-Me₂Ph)AgPPh₃)]ClO₄ (9) together with the tetranuclear complex [{Pt(C₆F₅)(bzq)(CN-2,6-Me₂Ph)Ag}₂](ClO₄)₂ (6) are emissive at room temperature showing bright greenish (7, 9) or yellowish (6) phosphorescence. In all three compounds a significant contribution of M' orbitals (AgPPh₃/Ag) to the frontier orbitals (FO) has been observed, and their main emissions seem to arise from mixed excited states 3ILCT (π-π' (bzq))/3MM'LCT (Pt/AgPPh₃ → bzq) (7, 9) or 3LMM'CT [(bzq) → Pt/Ag]/3ILCT [π-π' (bzq)] (6) in nature.