Phenyl argentate aggregates [Ag_nPh_n+1]⁻ (n = 2–8): Models for the self-assembly of atom-precise polynuclear organometallics

Electrospray ionization of phenyl argentates formed by transmetalation reactions between phenyl lithium and silver cyanide provides access to the argentate aggregates, [Ag_nPh_n+1]⁻, which were individually mass-selected for n = 2–8 in order to generate their gas-phase Ultraviolet Photodissociation (UVPD) “action” spectra over the range 304–399 nm. A strong bathochromic shift in optical spectra was observed with increasing size/n. Theoretical calculations allowed the assignment of the experimental UVPD spectra to specific isomer(s) and provided crucial insights into the transition from the 2D to 3D structure of the metallic component with the increasing size of the complex. The [Ag_nPh_n+1]⁻ aggregates contain neither pronounced metallic cluster properties nor ligated metallic cluster features and are thus not superatom complexes. They therefore represent novel organometallic characteristics built from Ag₂Ph subunits.