Four rhenium(I) complexes, [Re(CO) 3 Br(L n )] (n = 1-4), [L n = (4-fluorophenyl)pyridin-2-ylmethyleneamine (L 1 ), (4-chlorophe nyl)pyridin-2-ylmethyleneamine (L 2 ), (4-bromophenyl)pyridin-2-ylmethyleneamine (L 3 ), and (4-iodophenyl)pyridin-2-ylmethylenea mine, (L 4 )] have been synthesized and characterized by CHN analyses, 1 H, 13 C-NMR, IR, and UV-vis spectroscopy. The molecular structure of [Re(CO) 3 Br(L 1 )] is a distorted octahedron around rhenium with one Br, facial arrangement of three COs, and one diimine. UV-vis absorption and emission properties of the complexes have been studied at room temperature and the redox potentials are approximately insensitive to the substituent on the phenyl ring of ligands.