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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′-p-methoxyphenyl-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)2). 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 13+–53+ display broad and intense absorptions between 1000 and 3000 nm. Complexes 13+ and 23+ 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 33+–53+. Three-state theory has been used to explain this difference. The one-electron oxidized forms, 13+–53+, 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 12+–52+ to characterize their electronic structures and rationalize the absorption spectra in a wide energy range. DFT computations on 13+–53+ show that both ruthenium ions and the bridging ligand have comparable spin densities. TDDFT computations on 13+ and 43+ have been performed to complement the experimental results. [ABSTRACT FROM AUTHOR]