Complexes [Pt(C₆F₅)(bzq)L] {bzq = 7,8-benzoquinolinate; L = PPh₃ (2), pyPh₂ (3), tht (4), MeCN (5)} are prepared by replacing the acetone ligand in [Pt(C₆F₅)(bzq)(Me₂CO)] (1) with the corresponding L. The structures of complexes 2, 3 and 4 have been established by X-ray diffraction. Despite their neutral nature, complexes 1-5 react with AgClO4 in 2:1 molar ratio giving the corresponding trinuclear [{Pt(C₆F₅)(bzq)L}₂Ag]ClO4 {L = Me₂CO (6), PPh₃ (7), pyPh₂ (8), tht (9), MeCN (10)} which contain Pt→Ag dative bonds. The structures of complexes 7, 9 and 10 have been established by X-ray diffraction and confirm the existence of the Pt-Ag bonds (ca. 2.8 Å) and short η¹ bonding Ag-C interactions with the C_ipso of the bzq (ca. 2.4 Å). Moreover, complexes 3, 4, 7, 9 and 10 show intermolecular π···π interactions between the aromatic rings of the bzq ligands (separations of ca. 3.5 Å). The reactions of 1-5 with [Ag(PPh₃)(OClO₃)] in 1:1 molar ratio proceed with interchange of ligands between the metals and formation of [{Pt(bzq)(C₆F₅)(PPh₃)}₂Ag]ClO4 (7) and [AgL₂]ClO4 (X-ray). Only in the case of L = pyPh₂ (3), the dinuclear complex [(C₆F₅)(bzq)(PPh₃)PtAg(pyPh₂)]ClO4 (11) has been identified and its structure determined by X-ray diffraction. 11 contains a Pt→Ag (2.8147(1) Å) and a η¹-Ag-C_ipso(bzq) interaction(2.293(1) Å). The electronic absorption and luminescence behaviours of 1-11 have been investigated. The lower lying absorption bands of the mononuclear complexes are ascribed to ligand-centered [¹IL, π-π* (bzq)] character mixed with some metal-to-ligand charge transfer [¹MLCT (5d(Pt)→π*(bzq)]. For the trinuclear complexes are assigned to ¹ILCT/ ¹MM'LCT [π-π*(bzq)]/ (d/s(Pt,Ag)→π*(bzq)] transitions and to mixed ¹MLCT/¹L'LCT [MLCT (5d(Pt)→π*(bzq)]/ [L'LCT, Arf→ bzq] for the dinuclear complex 11, on the bases of Time-Dependent Density Functional Theory (TD-DFT) calculations carried out on 2, 4, 5, 9, 10 and 11Me in CH₂Cl₂. Only 2 and the heteronuclear compounds are emissive in the solid state at room temperature, however all of them are emissive at 77K (solid and glasses). The main phosphorescent emission seems in each case to be due to a transition similar in character to the lowest energy electronic absorption