Single crystals of [Ag(CN)(2)(-)]/NaCl and [Ag(CN)(2)(-)]/KCl show luminesc
ence spectra that change drastically with temperature. The major luminescen
ce band at 12 K is a UV emission at about 315 nm. Blue-green emissions in t
he 400-520 nm region appear upon an increase in temperature to 80 K. A furt
her increase in temperature results in the disappearance of the blue-green
emissions and the appearance of a high-energy UV emission at about 290 nm.
The color changes are reversible and represent a new example of luminescenc
e thermochromism. A kinetic model is proposed to show the radiative and non
radiative pathways at different temperatures. Highly resolved emission spec
tra are obtained upon a careful selection of the excitation wavelength. Ind
ividual peaks within the resolved emission bands are attributed to differen
t geometrical isomers of a given *[Ag(CN)(2)(-)](n) cluster in the alkali h
alide lattices. The wide range of luminescence energy, the strong luminesce
nce at ambient temperature, and the control of the profile of the emission
spectra by controlling the excitation wavelength are desired properties for
the design of new solid-state photonic devices based bn the Ag(I) luminesc
ence.