Detalhes bibliográficos
Ano de defesa: |
2014 |
Autor(a) principal: |
Silva, Cristiana da [UNESP] |
Orientador(a): |
Não Informado pela instituição |
Banca de defesa: |
Não Informado pela instituição |
Tipo de documento: |
Tese
|
Tipo de acesso: |
Acesso aberto |
Idioma: |
por |
Instituição de defesa: |
Universidade Estadual Paulista (Unesp)
|
Programa de Pós-Graduação: |
Não Informado pela instituição
|
Departamento: |
Não Informado pela instituição
|
País: |
Não Informado pela instituição
|
Palavras-chave em Português: |
|
Link de acesso: |
http://hdl.handle.net/11449/110714
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Resumo: |
The main goal of this work was to synthesize new homo- and heterometallic supramolecular structures with molecular recognition properties self-assembled from metal ions and exodentate ligands. The first part involved the preparation and spectroscopic characterization of polynuclear homometallic complexes obtained from self-assembly reactions between angular subunits [PdCl2(N N)] {N N = N,N,N´,N´-tetramethylethylenediamine (tmen), 2,2´-bipyridine (bpy), 1,10-phenanthroline (fen)} and the tridentate ligand 1,3,5-tris(4- pyridyl)imidazole (tpyImz). The solids [{Pd(bpy)}6(tpyHImz)4]Cl12·6H2O (1B), [{Pd(tmen)}6(tpyHImz)4]Cl12·30·H2O (2B) e [{Pd(phen)}6(tpyHImz)4]Cl12·6H2O (3B) are air stable and sluble in dmso. The compound [Pd6(μ-Pz)6(μ-bpym)3] (4B) was self-assembled from the linear building block [Pd2(μ-bpym)Cl4] (bpym = 2,2’-bipyrimidine) and pyrazolate anion (Pz). These polynuclear species were characterized bi elemental analyses, IR and NMR spectroscopies and mass spectrometry (ESI-MS). From the inspection of spectroscopic data and DFT calculations, structural models for compounds 1B-4B were proposed. For complexes 1B-3B, it was suggested the formation of cyclic metallosupramolecules A2 6A3 4 in which six angular ditopic subunits [Pd(N N)]+2 (N N = tmen, bpy, phen) act as vertices whereas four tritopic subunits tpyHImz (A3 4) give rise to the sides of the nanostructure. In the case of 4B, it is expected a hexanuclear triangular-shaped metallomacrocycle (A2 6L4 3) in which the core “Pd(μ-Pz)2Pd” acts as vertices of the triangle whereas the sides are composed by three bischelating 2,2’-bipyrimidine ligands. The second part of this work was carried out in collaboration with Universidade de Barcelona. A series of heterometallic metallamacrocycles have been constructed from self-assembly reactions between the Au(I) organometallic compounds [(AuPy)2(μ2-diphosphane)] {diphosphane = 1,2-bis(diphenylphosphanyl)ethane (dppe), ... |