The synthesis and spectroscopic properties of new cyclam-type ligands 5,7-dimethyl-6-R-1,4,8,1 1-tetraazacyclotetradecane (L), where R is a pendant chromophore such as an anthracene derivative, are reported. These ligands were prepared according to a nickel(II) template procedure, and the X-ray crystal structures of several Ni(II) intermediates are described. Reaction of the free base ligands L with CrCl(3)center dot 3THF resulted in facile formation of trans-[Cr(L)Cl-2]Cl complexes, and the structures and spectroscopic characterizations of these complexes are also described. Examination of the photophysical properties of trans-[Cr(L)Cl-2]Cl solutions at 77 K demonstrated the emission spectra to be dominated by phosphorescence from the ligand field doublet of the chromium(III) center. This also applies to the Cr(III) complex trans-[Cr(mac)Cl-2]Cl, where mac is the anthracene derivative 5,7-dimethyl-6-anthracenylcyclam. Excitation into the pi-pi* states of the anthracene leads to marked quenching of the fluorescence from this chromophore and sensitized phosphorescence from the metal-centered doublet state.