Presence or Absence of a Central Se Atom in Silver Selenide/Selenolate Clusters with Halite Topology: Syntheses and Properties of [(Ph3PAg)(8)Ag-6(mu(6)-Se)(1-x/2)(SePh)(12)](x+) (x=0, 1)

Two types of Ph3P/Ph ligated Ag14Se13-x (x = 0, 0.5) clusters with halite topology were synthesized that differ by the occupation/nonoccupation of the central position by a 13th Se atom and the resulting charge: neutral [(Ph3PAg)(8)Ag-6(mu(6)-Se)(SePh)(12)]center dot 11THF (1) and ionic [(Ph3PAg)(8)Ag-6(mu(6)-Se)(0.5)(SePh)(12)][R3SnCl2]center dot nTHF (R = Ph, n = 6 (2a); Cy, n = 5 (2b)) are all based on a tetradecanuclear cluster. The structural response on the charge was rationalized by DFT calculations, and the optical absorption behavior was studied.