Presence or absence of a central Se atom in silver selenide/selenolate clusters with halite topology: syntheses and properties of [(Ph(3)PAg)(8)Ag(6)(mu(6)-Se)(1-x/2)(SePh)(12)](x+) (x = 0, 1).

Two types of Ph(3)P/Ph ligated Ag(14)Se(13-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 [(Ph(3)PAg)(8)Ag(6)(mu(6)-Se)(SePh)(12)].11THF (1) and ionic [(Ph(3)PAg)(8)Ag(6)(mu(6)-Se)(0.5)(SePh)(12)][R(3)SnCl(2)].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.