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Dinuclear silver(I) complexes have recently gained attention for potential applications in visible light photochemistry. Our group has demonstrated that strong visible light absorption can occur in silver(I) dimers featuring redox-active naphthyridine diimine (NDI) ligands, resulting from a combination of close silver–silver interactions and low-lying ligand π* orbitals. A shortcoming of this previous work is that the sliver-NDI complexes displayed fluxional behavior due to rapid ligand exchange in solution; the ability to produce silver(I) dimers with targeted properties that maintain well-defined structures in solution remains an unmet challenge. Here, we describe the synthesis and characterization of a series of silver(I) dimers with naphthyridine-derived ligands, in which the ligand scaffold is systematically varied in order to determine structure/property relationships. We find that truncation of the NDI framework into an asymmetric “L-shaped” design results in a family of ligands that reliably produce structurally analogous silver(I) dimers. Ligands that maintain the π-conjugation of the iminopyridine motif consistently give silver(I) dimers with visible light absorption due to metal–metal to ligand charge transfer (MMLCT) transitions, and introduction of anionic (X-type) sites further increases stability in solution.