From Monomers to Geometry-Constrained Molecules: One Step Further Toward Cyanide Bridged Wires

PABLO ALBORÉS; LEONARDO D. SLEP; LIVIA S. EBERLIN; YURI E. CORILO; MARCOS N. EBERLIN; GUILLERMO BENITEZ; MARIA E. VELA; ROBERTO C. SALVAREZZA; LUIS M. BARALDO

INORGANIC CHEMISTRY

American Chemical Society

Año: 2009 vol. 48 p. 11226 - 11235

0020-1669

We report on the synthesis and properties of a family of linear cyanide bridged mixed-valence heptanuclear complexeswith the formula: trans-[L4RuII{(μ-NC)FeIII(NC)4(μ-CN)RuIIL04(μ-NC)FeIII(CN)5}2]6- (with L and L0 a para substitutedpyridine). We also report on the properties of a related pentanuclear complex. These oligomers were purifiedby size exclusion chromatography, characterized by electrospray ionization (ESI) mass spectrometry and elementalanalysis, and their linear shape was confirmed by scanning tunneling microscopy (STM). These complexes present arich electrochemistry associated with the seven redox active centers. The redox potential split of identical fragmentsindicates that there is considerable communication along the cyanide bridged backbone of the compounds, even forcenters more than 3 nm apart. This small attenuation of the interaction at long distances make these cyanide bridgedcompounds good candidates for molecular wires. Interestingly, the extent of the communication depends on therelative energy of the fragments, as evaluated by their redox potentials, providing a guide for improvement of thisinteresting property.