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Two ruthenium atoms are covalently connected to the para positions of a phenyl ring in 1,2,4,5-tetra(2-pyridyl)benzene (tpb) to form a linear Ru-tpb-Ru arrangement. This unique structure leads to appealing electronic properties for the biscyclometalated complex (tpy)Ru(tpb)Ru(tpy)(2+), where tpy is 2,2';6',2″-terpyridine. It could be stepwise oxidized at substantially low potential (+0.12 and +0.55 V vs Ag/AgCl) and with a noticeably large comproportionation constant (1.94 × 10(7)). In addition to the routinely observed metal-to-ligand charge-transfer transitions, (tpy)Ru(tpb)Ru(tpy)(2+) displays a separate and distinct absorption band at 805 nm with appreciable absorptivity (ε = 9000 M(-1) cm(-1)). This band is assigned to the charge transition from the Ru-tpb-Ru motif to the pyridine rings of tpb with the aide of density functional theory (DFT) and time-dependent DFT calculations. Complex (tpy)Ru(tpb)Ru(tpy)(2+) was precisely titrated with 1 equiv of cerium ammonium nitrate to produce (tpy)Ru(tpb)Ru(tpy)(3+), which shows intense multiple NIR transitions. The electronic coupling parameters H(ab) of individual NIR components are determined to be 5812, 4942, 4358, and 3560 cm(-1). DFT and TDDFT calculation were performed on (tpy)Ru(tpb)Ru(tpy)(3+) to elucidate its electronic structure and spin density population and the nature of the observed NIR transitions. Electron paramagnetic resonance studies of (tpy)Ru(tpb)Ru(tpy)(3+) exhibit a discernible rhombic signal with the isotropic g factor of ⟨g⟩ = 2.144. These results point to the strong orbital interaction of tpb with metal centers and that tpb behaves as a redox noninnocent bridging ligand in (tpy)Ru(tpb)Ru(tpy)(2+). Complex (tpy)Ru(tpb)Ru(tpy)(3+) is determined to be a Robin-Day class III system with full charge delocalization across the Ru-tpb-Ru motif.
Yao et al. (Thu,) studied this question.