By deprotonation reaction of the rhenium(I) tricarbonyl complex, ClRe(CO) 3 (H 2 bpydt) (2, H 2 dpydt=2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylic acid, our previous work in J. Organomet. Chem. 694 (2009) 763), complex 3, [Bu 4 N][ClRe(CO) 3 (Hbpydt)], is synthesized and characterized. Using 3 as the starting material, two trinuclear heterometallic complexes M(MeOH) 4 [ClRe(CO) 3 (Hbpydt)] 2 ·2MeOH (M=Cu, 4; M=Mn, 5) are obtained. The crystal structures of 2–5 have been determined by X-ray crystallography. Complexes 4 and 5 are isostructural. Their absorption and emission properties are studied. The magnetic properties of complexes 4 and 5 have also been investigated.