Dirhenium(III,III) compounds Re-2(DMBA)(4)Cl-2 (1, DMBA = N,N'-dimethylbenzamidinate) and Re-2(DEBA)(4)Cl-2 (2, DEBA = N,N,N'-diethylbenzamidinate) were synthesized via molten reactions between Re-2(OAc)(4)Cl-2 and the corresponding amidine. Re-2(DMBA)(4)(NO3)(2) (3) was obtained through reacting Re-2(DMBA)(4)Cl-2 with AgNO3. Single crystal X-ray diffraction studies revealed that the Re-Re distances in compounds 1-3 are 2.212(1), 2.217(1), and 2.173(1) Angstrom, respectively, which are consistent with the presence of a Re-Re quadruple bond. Voltammetric studies revealed that compound 2 exhibits two quasireversible couples, an oxidation and a reduction, and an irreversible reduction, while compound 1 displays irreversible couples at similar potentials. The three complexes exhibit (1)deltadelta* absorption as a shoulder at similar to440 nm ( epsilon similar to1500 M-1 cm(-1)). Upon excitation of solid samples or CH2Cl2 solutions of 2 with visible light, emission is observed at 824 nm (77 K) and 833 nm (298 K), respectively. The luminescence is assigned as arising from the 3deltadelta* excited state.