A new cyano-bridged dimeric oxo-centered triruthenium complex [{Ru-3(mu(3)-O)(mu-CH3COO)(6)(py)(2)}(mu-CN){Ru-3(mu(3)-O)(mu-CH3COO)(6)(py)(Lpy-ss)}](+) (py = pyridine, Lpy-ss = (C5H4N-CH2NHC(O)(CH2)(4)CH(CH2)(2)SS) ([1](+)) has been prepared, characterized, and confined on an Au(111) surface to form self-assembled monolayers (SAMs) (1/Au). The redox and IR spectroscopic properties observed for the discrete ions are essentially preserved in its SAMs. The molecules of SAMs 1/Au stand up with the cyano groups tilted to the gold surface. The electronic structures of 1/Au in different oxidation states have been studied by in situ infrared spectroscopy monitoring the stretching modes of the cyano group. The extent of cyano-mediated electronic communications between two triruthenium units in the SAMs has been successfully tuned by simply changing the electrolyte solutions from 0.1 M n-Bu4NPF6-CH2Cl2 to aqueous 0.1 M HClO4. (C) 2013 Elsevier B.V. All rights reserved.