Theoretical and experimental study on supramolecular structures obtained with trinuclear ruthenium clusters and porphyrins
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| Author(s): |
André Luiz Barboza Formiga
Total Authors: 1
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| Document type: | Doctoral Thesis |
| Press: | São Paulo. |
| Institution: | Universidade de São Paulo (USP). Conjunto das Químicas (IQ e FCF) (CQ/DBDCQ) |
| Defense date: | 2005-09-05 |
| Examining board members: |
Henrique Eisi Toma;
Alzir Azevedo Batista;
Sérgio de Paula Machado;
Mauro Carlos Costa Ribeiro;
Paulo Sérgio Santos
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| Advisor: | Henrique Eisi Toma |
| Abstract | |
The supramolecular chemistry of porphyrins and trinuclear ruthenium clusters has been investigated by a theoretical-experimental approach. Through the development of a new methodology based on theoretical tools, their relevant properties were explained using quantum mechanics, disclosing the electronic mechanisms by which coordination compounds modify the properties of porphyrin rings. Geometries, dynamics and electronic structures of these systems have been obtained by the development of new parameters for empirical force fields, and through semiempirical and ab initio methods. They have been used to explain the physical-chemical properties as, for example, the intermolecular association in solution, and thin film formation over flat surfaces. According to the detailed theoretical study coordination compounds increase the catalytic activity of porphyrin rings via π-orbital coupling, and this is the main mechanism of porphyrin activation. Such enhanced activity has been experimentally observed in photoelectrochemical devices and in the oxidation catalysis of organic substrates, providing synthetic models of cytochrome P-450 systems. (AU) | |