Presented here is the chemistry of Cr-III alkynyl complexes based on the rac-HMC and meso-HMC ligands (HMC = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Thus far, two pairs of cis/trans-[Cr(rac/meso-HMC)(C2R)(2)]Cl (R = Ph, C2H/C2SiMe3) complexes have been synthesized from reactions between cis/trans-[Cr(rac/meso-HMC)Cl-2]Cl and LiC2R. These complexes were characterized using single crystal X-ray diffraction, UV-vis spectroscopy, FT-IR spectroscopy, and fluorimetry. Single crystal X-ray diffraction studies revealed that these complexes adopt a pseudo-octahedral geometry. The electronic spectra of both the cis- and trans-[Cr(rac/meso-HMC)(C4R')(2)]Cl (R' = H or SiMe3) complexes exhibit d-d bands with pronounced vibronic progression associated with the asymmetric stretch of the Cr-bound C=C bonds. All of these complexes are phosphorescent and show structured emissions originating from the ligand field excited states.