Electronic and Magnetic Communication in Mixed-Valent and Homovalent Ruthenium Complexes Containing Phenylcyanamide Type Bridging Ligands

Abstract

Four new phenylcyanamido-bridge dinuclear ruthenium complexes [{Ru(tpy)(thd)}2(mu-L)] with tpy = 2,2':6',2' '-terpyridine, thd = 2,2,6,6-tetramethyl-3,5-heptanedione and L = dcbp = 4,4'-dicyanamidobiphenyl; bcpa = bis(4-cyanamidophenyl)acetylene; bcpda = bis(4-cyanamidophenyl)diacetylene; bcpea = 9,10,-bis(4-cyanamidophenylethynyl)anthracene have been prepared and fully characterized. The mixed valent Ru(II)Ru(III) and homovalent paramagnetic Ru(III)Ru(III) forms of all the complexes were electrochemically generated and studied by UV-vis-NIR and EPR spectroscopy. Electronic communication was quantified by the electronic coupling parameter V(ab) extracted from intervalence measurements in the near IR area, and magnetic communication was quantified in terms of the exchange coupling constant J, accessible from the intensity of the EPR signal when varying the temperature. Exponential decays for both electronic and magnetic coupling versus intermetallic distance were obtained and discussed.