The syntheses, spectroscopic properties, redox chemistry, and solid-state structures of products obtained from the reaction of Re 2 Cl 4 (dppm) 2 (dppm = bis(diphenylphosphino) methane) with the polycyano acceptors TCNQ (7,7,8,8tetracyanoquinodimethanido) and DM-DCNQI (2,5-dimethyl-N,NЈ-dicyanoquinonediimine) are described. The compounds [Re 2 Cl 4 (dppm) 2 ] 2 (µ-TCNQ), 1, and [Re 2 Cl 4 (dppm) 2 ] 2 (µ-DM-DCNQI), 2, have been prepared by reaction of two equivalents of Re 2 Cl 4 (dppm) 2 with TCNQ and DMDCNQI, respectively, in THF or CH 2 Cl 2 . A single-crystal X-ray crystallographic study of [Re 2 Cl 4 (dppm) 2 ] 2 (µ-TCNQ)ؒ10THF revealed the presence of a trans-µ 2 bidentate mode for the bridging TCNQ ligand that joins two Re 2 Cl 4 (dppm) 2 molecules through equatorial positions. In a similar fashion, the compound [Re 2 Cl 4 (dppm) 2 ] 2 (µ-DM-DCNQI)ؒ10THF consists of two Re 2 units coordinated to the two nitrile positions of the DM-DCNQI ligand. The electronic properties of both compounds are unusual in that they exhibit intense, broad absorptions that span the near-IR region and extend into the mid-IR. The electrochemistry of the compounds consists of numerous oxidation and reduction processes in the range of ϩ2.0 to Ϫ2.0 V as determined by cyclic voltammetry. Both 1 and 2 exhibit temperature independent paramagnetism (TIP) with large χ TIP values of 7.29 × 10 Ϫ3 and 6.23 × 10 Ϫ3 emu mol Ϫ1 , respectively.