The crown ether-linked iridium(III) complex [lr(ppy)(2) (di-aza-phen)](+) (1) {ppy = 2-phenylpyridine and di-aza-phen = 4,7-di(1,4-dioxa-7,13-dithia-10-azacyclopenta-dec-10-yl)-1,10-phenanthro line (7)} has been prepared. Compound 1 exhibits a notable luminescence enhancement in the presence of Ag+ in aqueous media. The analogous ruthenium(II) complex [Ru(phen)(2)(di-aza-phen)](2+) (4) {phen = 1,10-phenanthroline}, although equally exhibiting a luminescence enhancement in the presence of Ag+, is a far inferior sensor for Ag+ than 1. The 10 times higher luminescence enhancement (/ - /(0))/(0) of 1 was attributed to a dominance of the emission involving the di-aza-phen ligand that is responsible for binding to the metal ion. In contrast, the (MLCT)-M-3 emission of 4 does not involve the di-aza-phen ligand but does involve the phen ligand, thus only allowing for a remote effect upon addition of Ag+ ions. While 1 is a highly selective chemosensor for Ag+ in the presence of many metal ions, there is a strong interference of Hg2+ that may restrict its practical use.