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  • The Simple Yet Elusive Crystal Structure of Silver Acetate and theRole of the Ag−Ag Bond in the Formation of Silver Nanoparticlesduring the Thermally Induced Reduction of Silver Carboxylates
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  • The single crystal X-ray structure of silver acetate is reported. The Ag2(O2CCH3)2 repeating unit contains an Ag(I)−Ag(I) bond, as determined by Raman spectroscopy and DFT calculations. Calculations find that adding an electron to Ag2(O2CCH3)2 yields (Ag2)+• complexed unsymmetrically by two acetate ions.
  • We report the single-crystal X-ray structure of silver acetate, accompanied by Raman spectra anddensity functional theory calculations. This work should aid understanding of the process of formingsilver nanoparticles during the thermally induced reduction of silver carboxylates, e.g., in thermographicmaterials. The structure of silver acetate comprises the often-observed Ag2(carboxylate)2 dimer unitconnected by interdimer Ag−O bonds to form infinite chains that align in a parallel fashion, formingstacks. The presence in the dimer of a Ag−Ag bond via closed-shell d10−d10 interactions is determinedby Atoms in Molecules methodology, tentatively supported by the experimental observation of Ramanscattering peaks (also found by vibrational frequency calculations) for Ag−Ag stretching. The Ag(I)−Ag(I) bond may be an important precursor to metallic silver formation, as single-electron reduction ofthe Ag2(carboxylate)2 species could result in the formation of (Ag2)+•, known in photographic chemistryas a precursor to metallic silver clusters. The calculated structure of the radical anion of silver acetateconsists of a (Ag2)+• cluster complexed by two acetate ions, lending support to earlier postulates thatAg−Ag bonding may promote the formation of silver nanoparticles during the thermally induced reductionof silver carboxylates.
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