The electrochemical and photophysical properties of [(X-tpy)RuII(tpy-(fc)2-tpy)RuII(X-tpy)]4+ (tpy = terpyridyl; X = −H (1a), −OCH3 (1b), −Cl (1c); fc = ferrocenyl) and [(X-tpy)RuII(tpy-CC-(fc)2-CC-tpy)RuII(X-tpy)]4+ (X = −H (2a), −OCH3 (2b), −Cl (2c)) are described. The ground-state HOMO and LUMO energies were probed by electrochemical measurements. The excited-state photophysical properties were probed by UV–vis absorption spectroscopy and luminescence spectroscopy. Complexes of 1a−c are nonemissive (λexc 480–580 nm) in deoxygenated pure CH3CN or H2O/CH3CN (4/1) solution at 25 °C. Complexes 2a−c have room-temperature luminescence in H2O/CH3CN (4/1) solution. On comparison of the luminescent properties of 2b,c with those of 2a, the attachment of −OCH3 and −Cl substitutents causes a decrease of luminescence quantum yields and triplet lifetimes.
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