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Doctoral Thesis
DOI
10.11606/T.46.1994.tde-19082010-102939
Document
Author
Full name
Koiti Araki
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 1994
Supervisor
Committee
Toma, Henrique Eisi (President)
Iamamoto, Yassuko
Paoli, Marco Aurélio de
Politi, Mário José
Temperini, Marcia Laudelina Arruda
Title in Portuguese
Propriedades supramoleculares de porfirinas polinucleares
Keywords in Portuguese
Complexos de rutênio
Compostos organometálicos
Porfirinas
Quimica inorgânica
Química supramolecular
Abstract in Portuguese
A síntese e a caracterização de uma série de porfirinas polinucleares, por meio de análise elementar, espectroscopia eletrônica e Raman ressonante, voltametria cíclica e espectroeletroquímica, são apresentadas nesta tese. Estas supermoléculas foram obtidas pela coordenação de quatro grupos Ru(edta)- ou Ru(bipY)2Cl+ aos resíduos piridínicos das meso-tetra(piridil)porfirinas base-livre e metaladas. As propriedades eletrocatalíticas, fotoquímicas e fotofísicas foram estudadas, dando especial atenção às propriedades supramoleculares resultantes da interação entre as porfirinas e os complexos de rutênio periféricos. Também, foi explorada a capacidade singular desses complexos de formar filmes. Estes materiais são excelentes condutores iônicos e eletrônicos, e se comportam como fotocondutores moleculares, possibilitando a conversão de energia luminosa em elétrica. A possibilidade de utilizar estes filmes na confecção de dispositivos, tais como retificadores, amplificadores e transístores, assim como, células fotoelétricas e fotoeletroquímicas, abre novas perspectivas na área da fotoeletrônica molecular.
Title in English
Supramolecular properties of polynuclear porphyrins
Keywords in English
Inorganic chemistry
Porphyrins
Ruthenium complexes
Supramolecular chemistry
Abstract in English
The synthesis and characterization of a series of polynuclear porphyrins by elementary analysis, electronic and resonance Raman spectroscopy, cyclic voltanunetry and spectroelectrochemistry, are presented. Those supermolecules were obtained by attaching Ru( edta)- or Ru(bipY)2Cl+ groups to the four pyridine residues of the free-base or the metallated meso-tetra(pyridil)porphyrins. Their electrocatalytical, photochemical and photophysical properties were studied. Special attention were paid to the supramolecular properties resulting from the interaction of the porphyrin and the peripheral ruthenium complexes. The unusual ability of these complexes to form stable films was also explored. These materials are excellent ionic and electronic conductors and act as molecular photoconductors, converting light into electricity. The films can be used for the design of electronic devices such as rectifiers, amplifiers and transistors, as well as, of photoelectric and photoelectrochemical cells.
 
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Publishing Date
2010-08-20
 
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