The electrochemical and spectroscopic properties of eight bis(tridentate) cyclometalated Ru(II)compounds covalently linked by a phenyl- or xylyl-thiophene bridge to a pendant triphenylamine (TPA) were characterized in fluid solution and immobilized on metal oxide surfaces. Upon surface immobilization, the TPA(+/0) reduction potentials of the phenyl-bridged compounds exhibited large changes, +/- 100 mV, relative to solution-based values, yet those observed for the xylyl-bridged compounds were relatively unchanged. The highest occupied molecular orbital of the surface-immobilized compounds was associated with either TPA or R-II, enabling the study of the electron transfer in opposite directions. Electron transfer in the mixed-valent states of the compounds was found to proceed by different optical pathways for Ru-II -> TPA(+) relative to TPA -> Ru-III. Mulliken-Hush analysis of intervalence charge transfer bands for the phenyl-bridged compounds revealed that the electronic coupling matrix element, H-DA, was similar to 950 cm(-1) for Ru-II -> TPA(+) , while H-DA for TPA -> Ru-III appeared to be 2500 cm(-1). In contrast, the xylyl-bridged compounds were weakly coupled. A superexchange analysis, where unoccupied bridge orbitals were taken directly into account, led to a very different conclusion: HDA did not depend on the charge-transfer direction or path. The results imply that the electron-transfer direction can alter optical charge transfer pathways without influencing the electronic coupling.