Ruthenium Complexes with Strongly Electron-Donating Terpyridine Ligands: Effect of the Working Electrode on Electrochemical and Spectroelectrochemical Properties

摘要: The combination of 2,2ʹ:6ʹ,2″-terpyridines (tpy) and RuII is known to deliver molecular supramolecular assemblies with remarkable properties. We present here new complexes modified tpy ligands substituted varying numbers dimethlyamino groups. Electrochemistry shows that the incorporation strongly electron-donating groups on leads a negative shift oxidation potential by close 1 V. reductive electrochemical responses are dependent nature working electrode, glassy carbon gold electrodes showing best results. These observations led us develop Optically Transparent Thin Layer Electrochemical (OTTLE) cell, based electrode. use UV-vis-NIR spectroelectrochemical results OTTLE together simulations cyclic voltammograms, allow characterize four reduction steps in these complexes, final two which lead bond activations at ruthenium center. This observation our knowledge unprecedented coordinatively saturated type [Ru(tpy)2]2+. various redox states were characterized EPR spectroelectrochemistry through DFT calculations. presented establish as highly attractive coordination chemistry, display utility gold-based cell for measurements.