Arylethynylchromium(III) complexes of the form trans-[Cr(cyclam)(CCC(6)H(4)R)(2)]OTf (where cyclam = 1,4,8,11-tetraazacyclotetradecane, R = H, CH(3), or CF(3) in the para position, and OTf = trifluoromethanesulfonate) have been prepared and characterized by IR spectroscopy and X-ray diffraction. The complexes are emissive with excited-state lifetimes in a deoxygenated fluid solution between 200 and 300 micros.