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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Symmetrical binuclear ruthenium compounds : synthesis , characterization and study of electronic communication / Compostos binucleares simÃtricos de rutÃnio: sÃntese, caracterizaÃÃo e estudo de comunicaÃÃo eletrÃnica

Natanna Azevedo de Aguiar 16 June 2015 (has links)
CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / No trabalho descrito a seguir, serÃo apresentados e discutidos os resultados das sÃnteses e caracterizaÃÃes de quatro compostos inÃditos, a citar: trans-[Ru(NH3)4(4-Apy)(pyS)]Cl2 (1), trans-[Ru(NH3)4(pyS)(iTna)]Cl2 (2), trans-{[Ru(NH3)4(pyS)]2-Â-4-Apy}(PF6)4 (3) e trans-{[Ru(NH3)4(pyS)]2-Â-iTna}(PF6)4 (4), onde pyS = 4-mercaptopiridina, 4-Apy = 4-aminopiridina e iTna = isotionicotinamida. O grau de comunicaÃÃo eletrÃnica entre os centros metÃlicos nos complexos binucleares foi avaliado por eletroquÃmica e apresentaram valores de constante de comproporcionamento (KC) de 2,058 x 104 e 4,848 x 104 quando 4-Apy e iTna foram usados, respectivamente, como ligantes pontes. Considerando que os ligantes 4-Apy (4,33 Ã) e iTna (5,17 Ã) apresentam dimensÃes similares, o maior grau de deslocalizaÃÃo eletrÃnica entre os centros metÃlicos observado para o ligante iTNA Ã atribuÃdo a maior rigidez desta espÃcie. Os complexos de valÃncia mista (RuII-RuIII), gerados a partir da oxidaÃÃo estequiomÃtrica dos complexos binucleares com K2S2O8, apresentaram bandas de intervalÃncia na regiÃo do infravermelho prÃximo (~ 1670 nm). A partir desta transiÃÃo, foi possÃvel calcular os parÃmetros de deslocalizaÃÃo eletrÃnica sendo observado valores de acoplamento entre os centros metÃlicos (Hab) da ordem de 210 cm-1. Este resultado, em conjunto com os dados eletroquÃmicos, permitiram classificar os sistemas isolados como sendo de Classe II, de acordo com a classificaÃÃo de Robin e Day. Os compostos binucleares isolados, por apresentarem comunicaÃÃo eletrÃnica moderada, sÃo considerados, portanto, potenciais precursores para a formaÃÃo de fios moleculares. Os resultados obtidos durante o desenvolvimento deste projeto foram apresentados no XVII Brazilian Meeting on Inorganic Chemistry (Anexo) e estÃo em fase final de compilaÃÃo para publicaÃÃo em periÃdico indexado. / The following work will deal on the results and discussions obtained from the syntheses and characterizations of four new compounds, to mention: trans-[Ru(NH3)4(4-Apy)(pyS)]Cl2 (1), trans-[Ru(NH3)4(pyS)(iTna)]Cl2 (2),trans-{[Ru(NH3)4(pyS)]2-μ-4-Apy}(PF6)4 (3) and trans-{[Ru(NH3)4(pyS)]2-μ-iTna}(PF6)4 (4), where pyS = 4-mercaptopyridine, 4-Apy = 4-aminopyridine and iTna = isothionicotinamide. The level of electronic communication between the metal centers in the binuclear compelxes was evaluated by means of electrochemistry and showed values of 2.058 x 104 and 4.848 x 104 when 4-Apy (4,33 Ã) and iTna (5,17 Ã) were used, respectively, as bridging ligands. Assuming that these species are of similar dimensions, the higher level of electronic communication between the metal centers observed for the iTna bridging ligand is assigned to the greater rigidity of this species. The mixed valence complexes (RuII-RuIII), produced from the stoichiometric oxidation by K2S2O8, showed intervalence transitions in the near infrared region (~ 1670 nm). The electron deslocalization parameters were calculated from these transitions and it was observed values of electron coupling between the metal centers (Hab) of about 210 cm1. This result, in conjunction with the electrochemical data, allowed the classification of the isolated systems as Class II according to the ranking of Robin and Day. The synthesized binuclear complexes, by presenting moderate electron communication, are considered,therefore, potential precursors for the assembling of molecular wires. The results obtained during the developing of this proposal were presented at the XVII Brazilian Meeting on Inorganic Chemistry (Annex) and are in the final compilation stage for publication in peer-reviewed journal.

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