The nature of the lowest energy excited states of the Ag2(dmb)2X2 complexes (X = Cl, Br, I; dmb = 1,8-diisocyano-ρ-menthane) have been addressed both experimentally and theoretically. It is shown that the lowest energy excited states of the complexes are charge transfer states from the silver-halide frame to the isocyanide ligands (M/XLCT) based upon UV-visible spectra and emission polarization ratio measurements, and extended Hückel molecular orbital calculations (EHMO). The metal-centered dσ* → pσ bands have been observed in the higher energy region of the spectra (232–242 nm). The complexes are luminescent (440 ≤ λe ≤ 480 nm) both in a glass and in the solid state at 77 K where the emission lifetimes, τe, range from 20 to 90 µs, which depend upon the nature of the halide (for the solid state data) and the media. No emission is observed at room temperature.
