The mononuclear [(DEAS-bpy)Re(CO)(3)(BPP)](+), [(DEAS-bpy)Re(CO)(3)(BPP-Me)](2+), and [(bpy)Re(CO)(3)(BPP)](+) and the binuclear [(DEAS-bpy)Re(CO)(3)(mu-BPP)Re(CO)(3)(DEAS-bpy)](2+) complexes have been prepared, and their electrochemical and photophysical properties have been investigated (DEAS-bpy = 4,4'-bis [p-(diethylamino)-alpha-styryl]-2,2'-bipyridine, BPP = 1,10-bis(4-pyridyl)-3,8-dimethyl-1,3,5,7,9-decapentaene, bpy = 2.2'-bipyridine), The electrochemical behavior of these complexes shows that reduction occurs first on the BPP ligand (E approximate to -0.85 V vs SCE) and then on the DEAS-bpy ligand (E approximate to -1.30 V). The site easier to oxidize is on the amines of the DEAS-bpy ligand (E approximate to +0.70 V); other oxidation processes occur at more positive potential on the ligands and on the metal center. The complexes containing both the DEAS-bpy and the BPP ligands phosphoresce in rigid matrix at 77 K from a (LC)-L-3 state of the DEAS-bpy ligand (lambda(max) approximate to 675 nm, tau > 350 mu s); no emission is observed at room temperature in fluid solution, where a long-lived (tau approximate to 4 mu s) species is observed through transient absorption measurements. By combining electrochemical and photophysical data, it is concluded that following light excitation a charge-separated state is formed, which is noticeably long-lived compared to that observed in other donor-acceptor complexes in homogeneous solution.