Self-assembled multilayer thin films have been prepared on Au and merc
aptosilanized glass substrates by alternate surface derivatization wit
h Cu2+ ion and alkanedithiols. The films deposited on glass show intri
nsic orange-red photoluminescence and were studied by fluorescence spe
ctroscopy. A strongly photoluminescent solid was also obtained by reac
tion of 1,6-hexanedithiol with cupric perchlorate in ethanolic solutio
n. Multilayer structures on Au were studied by ellipsometry and X-ray
photoelectron spectroscopy (XPS). Both in the solid material and in th
e self-assembled thin films, XPS measurements suggest Cu is present in
the +1 oxidation state. This was also confirmed by cyclic voltammetry
of Cu ion adsorbed to a self-assembled monolayer of 1,6-hexanedithiol
on gold. Metal-metal interactions in the form of clustering might con
tribute to the unusual photophysical properties observed in both types
of materials.