Cyclometalated diruthenium complexes 1(PF6)(2)-5(PF6)(2) bridged by 1,3,6)8-tetra(pyrid-2-yl)-pyrene have been prepared, with the terminal ligand bis(N-methylbenzimidazolyl)pyridine (1 (PF6)(2)), 4'-di-(p-methoxyphenyl)amino-2,2':6';2,''-terpyridine (2(PF6)(2))-,4'-pmethoxyphenyl-2,2':6',2 ''-terpyridine (3(PF6)(2)), 2,2':6',2 ''-terpyridine (4(PF6)(2))) and trimethyl-4,4',4 ''-tricarboxylate-2,2':6 '',2 ''-terpyridine (5(PF6)). The single-crystal X-ray structure of 4(PF6)(2) is presented. These complexes show two stepwise anodic redox pairs, and the potentials progressively increase from 1(PF6)(2) to 5(PF6)(2). Complexes 1(PF6)(2)-4(PF6)(2) have comparable electrochemical potential splitting of 200-210 mV, while complex 5(PF6)(2) has a splitting of 170 mV. Upon one-electron oxidation by chemical oxidation or electrolysis, the resulting mixed-valent complexes 1(3+)-5(3+) display broad and intense absorptions between 1000 and 3000 nm. Complexes 1(3+) and 2(3+) show the presence of a higher-energy shoulder band in addition to the Main near-infrared absorption band. This shoulder band is less distinguished for 3(3+)-5(3+). Three-state theory has been used to explain this difference. The one-electron oxidized forms, 1(3+)-5(3+), exhibit rhombic EPR signals at 77 K with the isotropic g values in the range of 2.18-2.24. Density functional theory (DFT) and time-dependent DFT (TDDFT) computations have been performed on 1(2+)-5(2+) to characterize their electronic structures and rationalize the absorption spectra in a wide energy range. DFT computations on 1(3+)-5(3+) show that both ruthenium ions and the bridging ligand have comparable spin densities. TDDFT computations on 1(3+) and 4(3+) have been performed to. complement the experimental results.