Desenvolvimento de sistemas polinucleares baseados em clusters trinucleares e complexos poliimínicos de rutênio: unidades de montagem em química supramolecular / Development of polynuclear systems based on trinuclear cluster and polyimines ruthenium compounds: building blocks in supramoleular chemistry

AUTOR(ES)
DATA DE PUBLICAÇÃO

2002

RESUMO

The aim of the work reported is to develop polynuclear structures based on trinuclear ruthenium clusters. All the oligomers are seen as interesting options to the future development of supramolecular devices, due to their photophysical and electrochemical properties. A series of mixed dimers and one trimer were obtained by the combination of the [Ru3O(CH3COO)6(py)2(CH3OH)]+ cluster with [Ru(bpy)2(P)(L)]+ complexes (P = N-heterocyclic bridging ligand; L = P, Cl or CN). The NMR, cyclic voltammetry and spectroelectrochemical characterization of the dimers where L = Cl were used as a base to interpret the results collected for the other complexes; the data reflect a weak interaction between the units, depending on the electronic characteristics of the bridging ligand P. In the dimers where L = CN, occurs the quenching of the [Ru(bpy)2] emission by the cluster through a photoinduced electron transfer mechanism. For the cluster in its reduced form, it is suggested that an energy transfer process also occurs. On the second part of the Thesis, polycluster systems containing six and ten bridged cluster units are reported. The novel supermolecules present a series of multielectronic redox processes and, in this case, electronic communication among the metallic centers is more pronounced, depending on the clusters oxidation state.

ASSUNTO(S)

fotofísica inorgânica eletroquímica química supramolecular espectroscopia inorganic photophysics rmn ruthenium spectroscopy electrochemistry nmr supramolecular chemistry rutênio

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