Ruthenium molecular wires with conjugated bridging ligands: onset of band formation in linear inorganic conjugated oligomers |
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Authors: | Flores-Torres Samuel Hutchison Geoffrey R Soltzberg Leonard J Abruña Héctor D |
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Institution: | Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA. |
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Abstract: | We have prepared and characterized a series of multimetallic oligomers of Ru using the pi-conjugated bridging ligand tetra-2-pyridyl-1,4-pyrazine (tppz), as well as mixed-ligand complexes with terpyridine end caps, and analyzed their electrochemical and spectroscopic properties, comparing them with modern computational electronic structure methods. The results suggest that the high degree of metal-metal interunit communication in these linear oligomers yields low HOMO-LUMO gaps, high delocalization, and the onset of "quasi-band" features, all indicative that these compounds should be excellent molecular wire materials. Recent spectroscopic and excited-state analyses of these and related compounds focus on optically accessible states, which ignore optically silent frontier electronic states more relevant to nanoelectronic applications. |
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