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The photoexcitation of a triangular silver(I) hydride complex, [Ag3(μ3‐H)(μ2‐dcpm)3](PF6)2 ([P](PF6)2, dcpm=bis(dicyclohexylphosphino)methane), designed with "UV‐silent" bis‐phosphine ligands, provokes hydride‐to‐Ag3 single and double electron transfer. The nature of the electronic transitions has been authenticated by absorption and photodissociation spectroscopy in parallel with high‐level quantum‐chemical computations utilizing the GW method and Bethe–Salpeter equation (GW‐BSE). Specific photofragments of mass‐selected [P]2+ ions testify to charge transfer and competing pathways resulting from the unique [Ag3(μ3‐H)]2+ scaffold. This structural motif of [P](PF6)2 has been unequivocally verified by 1H NMR spectroscopy in concert with DFT and X‐ray diffraction structural analysis, which revealed short equilateral Ag–Ag distances (dAgAg=3.08 Å) within the range of argentophilic interactions. The reduced radical cation [P].+ exhibits strong oxophilicity, forming [P+O2].+,which is a model intermediate for silver oxidation catalysis. [ABSTRACT FROM AUTHOR]

Highlights from the article: Keywords: charge transfer; hydride ligands; mass spectrometry; metal-metal interactions; photochemistry; silver The unique [Ag SB 3 sb ( SB 3 sb -H)] SP 2+ sp scaffold, featuring argentophilic interaction, was unequivocally verified by SP 1 sp H NMR spectroscopy in concert with X-ray structural analysis and DFT. Photochemistry, mass spectrometry, silver, charge transfer, hydride ligands, metal-metal interactions.