In acetonitrile the rigid diphosphine ligand 2,9-bis(diphenylphosphino)-1,8-naphthyridine (dppn) reacts with (SMe2)-AuCl in the presence of NaPF6 to produce a pale-yellow material identified as [Au2Na(mu-dppn)(3)](PF6)(3) (1). In acetonitrile dppn reacts with 2 equiv of (SMe2)AuCl to form the simple Au-Cl adduct of the Ligand, Au(2)Cl(2)dppn (2). In a fashion analogous to that of the synthesis of 1, the reaction of equimolar AgNO3 with dppn produces the trimetallic species [Ag-2(mu-dppn)(3)Ag](PF6)(3) (3) as a bright-yellow material. 1, 2, and 3 were characterized by P-31{H-1} NMR spectroscopy, electronic absorption spectroscopy, X-ray crystallography, emission spectroscopy. and elemental analysis. Additionally 1 was further characterized by cyclic voltammetry and mass spectrometry, 1.4.5CH(3)CN . 0.5(C2H5)(2)O (C107H72Au2F18N10.5NaO) crystallizes in the triclinic space group P (1) over bar with a = 15.408(3) Angstrom, b = 17.295(3) Angstrom, c = 22.425(5) Angstrom, alpha = 73.68(1)degrees, beta = 77.32(1)degrees, gamma = 74.18(1)degrees, V = 5451.4(19) Angstrom(3), and Z = 2. C32H24Au2Cl2N2P2 (2) crystallizes in the monoclinic space group Cc with a = 10.936(2) Angstrom, b = 19.860(5) Angstrom, c = 20.864(2) Angstrom, beta = 118.182(1)degrees, V = 3127.3(8) Angstrom(3), and Z = 4. Compound 3 crystallizes as the bis-DMSO adduct (C101H84Cl2F18N6O2P9S2) in the monoclinic space group C2/c with a = 28.825(7) Angstrom, b = 17.013(3) Angstrom, c = 23.916(7) Angstrom, beta = 115.23(1)degrees, V = 10609.6(44) Angstrom(3), and Z = 4. The structures of 1 and 3 contain a three-coordinate metal capping the metallocryptate with an encapsulated ion. The central Ag(I) ion in 3 is positioned off-center to form a short Ag ... Ag interaction of 3.145(2) Angstrom, while the central Na+ ion of 1 is centrally positioned with long Au ... Na interactions of similar to 3.5 Angstrom. The solution-state properties of 1 were probed, 1 is emissive, as are the Li, K, and Cs analogues.