Reactions of 9,10-bis(diphenylphosphino) anthracene (PAnP) and AgX (X = OTf-, ClO4-, PF6-, and BF4-) led to luminescent Ag-PAnP complexes with rich structural diversity. Helical polymers [Ag(mu-PAnP)(CH3CN)X](n) (X = OTf-, ClO4-, and PF6-) and discrete binuclear [Ag-2(mu-PAnP)(2)(CH3CN)(4)](PF6)(2), trinuclear [Ag-3(mu-PAnP)(3)superset of BF4](-) (BF4)(2), and tetranuclear [Ag-4(mu-PAnP)(4)superset of(ClO4)(2)](ClO4)(2) metallacycles were isolated from different solvents. The tri- and tetranuclear metallacycles exhibited novel puckered-ring and saddlelike structures. Variable-temperature (VT) P-31{H-1}-NMR spectroscopy of the complexes was solvent dependent. The dynamics in CD3CN involve two species, but the exchange processes in CD2Cl2 are more complicated. A ring-opening polymerization was proposed for the exchange mechanism in CD3CN.