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

Abstract

Electrospray ionization of phenyl argentates formed by transmetallation reactions between phenyl lithium and silver cyanide provides access to the argentate aggregates, [AgnPhn+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 nm to 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 2D to 3D of the metallic component with the increasing size of the complex. The  these three authors contributed equally.

Modular Ion Mobility Calibrants for Organometallic Anions Based on Tetraorganylborate Salts

“…Accordingly, identical growth trends for [M n Ph n +1 ] − as well as for [Li n –1 M n Ph 2 n ] − ions as a function of n could be ascertained irrespective of the coinage metal M (Figure S10). While an approximately linear growth holds for the [M n Ph n +1 ] − species for n = 1–4, the addition of another [MPh] unit to [M 4 Ph 5 ] − leads to pentanuclear complexes with a more compact structure compared to the lower oligomers . Likewise, the pentanuclear [Li 2 M 3 Ph 6 ] − ions are denser than the corresponding lithium-bound dimers [LiM 2 Ph 4 ] − .…”