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

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)We report on the synthesis and properties of a family of linear cyanide bridged mixed-valence heptanuclear complexes with the formula: trans-[L(4)Ru(II){(mu-NC)Fe(III)(NC)(4)(mu-CN)Ru(II)L'(4)(mu-NC)Fe(III)(CN)(5)}(2)](6-) (with L and L' a para substituted pyrdine). We also report on the properties of a related pentanuclear complex. These oligomers were purified by size exclusion chromatography, characterized by electrospray ionization (ESI) mass spectrometry and elemental analysis, and their linear shape was confirmed by scanning tunneling microscopy (STM). These complexes present a rich electrochemistry associated with the seven redox active centers. The redox potential split of identical fragments indicates that there is considerable communication along the cyanide bridged backbone of the compounds, even for centers more than 3 nm apart. This small attenuation of the interaction at long distances make these cyanide bridged compounds good candidates for molecular wires. Interestingly, the extent of the communication depends on the relative energy of the fragments, as evaluated by their redox potentials, providing a guide for improvement of this interesting property.48231122611235University of Buenos AiresConsejo Nacional de Investigaciones Cientificas y Tecnicas (CONICET)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Quantum Chemistry and Mössbauer Spectroscopy

The underlying physics and analysis of Mössbauer spectra have been explained in detail in Chap. 4. In that chapter, the principles of how a spectrum is parameterized in terms of spin-Hamiltonian (SH) parameters and the physical origin of these SH parameters have been clarified. Many Mössbauer studies, mainly for 57Fe, have been performed and there is a large body of experimental data concerning electric- and magnetic-hyperfine interactions that is accessible through the Mössbauer Effect Database