Tris(2-pyridylemthyl)amine (TPA) derivatives having two amide moieties at the 6-positions of the two pyridine rings of TPA and their Ru(II) complexes were synthesized and characterized by spectroscopic methods, X-ray crystallography, and electrochemical measurements. The complexes prepared were [RuCl(L)]PF6 (L = N,N-bis(6-(1-naphthoylamide)-2-pyridylmethyl)-N-(2-pyridylmethyl)amine (1), N,N-bis(6-(2-naphthoylamide)-2-pyridylmethyl)N-(2-pyridylmethyl)amine (2), N,N-bis(6-(isobutyqamide)-2-pyridylmethyl)-N-(2-pyridylmethyl)amine (3)); the crystal structures of the three compounds were established by X-ray crystallography. In variable-temperature H-1 NMR spectra of 1 and 2 in CD3CN solutions, the pi-pi stacking in 1 was too rigid to exhibit any fluxional motions in NMR measurements; however, the pi-pi stacking of 2 was weaker and showed fluxional behavior in nearly T-shaped pi-pi interaction for the 2-naphthly groups (DeltaHdegrees = -2.3 kJ mol(-1); DeltaGdegrees = -0.9 kJ mol(-1) and DeltaSdegrees = -7.7 J mol(-1) K-1 at 233 K in CD3CN). For each of these three complexes, one of the amide moieties coordinated to the Ru(II) center through an amide oxygen. The other uncoordinated amide N-H formed intramolecular hydrogen bonding which remained intact even in aqueous media, indicating the intramolecular hydrogen bonding was geometrically compelled to form. The amide coordination is also stabilized and strengthened by the hydrogen bonding, so that the structure of each compound is maintained in solution. It is suggested that this hydrogen bonding lowers the redox potentials of the Ru(II) centers due to polarization of the coordinated amide C=O bond, in which the oxygen atom becomes more electrostatically negative and its electron-donating ability is strengthened. The N-H protons in the coordinated amide moieties were found to undergo a reversible deprotonation-protonation process, and the redox potentials of the Ru(II) centers could be regulated in the range of 500 mV in CH3CN solutions. The Pourbaix diagram for 1 clearly showed that this proton-coupled redox behavior is a one-electron/ one-proton process, and the pK(a) value was estimated to be similar to6.