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Doctoral Thesis
DOI
https://doi.org/10.11606/T.46.2020.tde-08112021-171031
Document
Author
Full name
Lais Sottili de Matos
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Paulo, 2020
Supervisor
Committee
Iha, Neyde Yukie Murakami (President)
Baader, Josef Wilhelm
Batista, Alzir Azevedo
Hara, Melina Kayoko Itokazu
Title in Portuguese
Óxidos nanoestruturados e complexos de Re(I) para dispositivos optoeletrônicos
Keywords in Portuguese
Complexo de Re(I)
Engenharia de fotoanodo
Filmes finos
Fotoisomerização trans-cis no visível
Abstract in Portuguese
Nessa tese foi realizada a implementação de camadas compactas em células solares sensibilizadas por corantes (Dye-sensitized Solar Cells - DSCs) para aumentar a eficiência dos dispositivos, bem como a investigação das propriedades fotoquímicas e fotofísicas de complexos de Re(I) para aplicação em dispositivos optoeletrônicos. Com base em princípios de engenharia de fotoanodo, um filme fino de TiO2/ZnO foi desenvolvido e aplicado como camadas compactas em DSCs, resultando na melhora da conversão de energia (até 67%) em comparação às DSCs típicas, levando, assim, a fabricação de dispositivos mais eficientes. Em paralelo, foram obtidos os complexos fac-[Re(CO)3(R2phen)(trans-stpyCOOMe)]+, em que R2phen = 1,10-fenantrolina 4,7-dissubstituídas e trans-stpyCOOMe = trans-4-(2-(4-piridinil)vinil)benzoato de metila, que apresentam fotoisomerização reversíveis: transcis e cistrans. As espécies cis são emissivas e possuem propriedades adequadas para fotossensores e fotochaveadores. Também foram sintetizados os complexos fac-[Re(CO)3(dcbH2)(trans-L)]+, em que dcbH2 = ácido 4,4-dicarboxi-2,2-bipiridina e trans-L = trans-4-estirilpiridina (trans-stpy) ou trans-1,2-bis(4-piridil)etileno (trans-bpe), que foram uns dos primeiros reportados na literatura a apresentaram fotoisomerização transcis no visível, até 436 nm, o que permite aplicação na conversão de energia. Em especial, o complexo fac- [Re(CO)3(dcbH2)(trans-stpy)]+ exibiu essa fotorreação quando adsorvido na superfície do TiO2, apresentando boas perspectivas em aplicações.
Title in English
Nanostructured oxides and Re(I) complexes for optoelectronic devices
Keywords in English
Photoanode engineering
Re(I) complexes
Thin film
Visible trans-to-cis photoisomerization
Abstract in English
In this thesis, compact layers were employed to increase the performance of dye-sensitized solar cells (DSCs), as well as the photochemical and photophysical properties of Re(I) complexes were investigated toward application in optoelectronic devices. The TiO2/ZnO thin film was judiciously engineered as compact layers for photoanodes in DSCs, resulting in a significant improvement (up to 67%) of the DSC energy conversion leading to efficient devices. In parallel, fac-[Re(CO)3(R2phen)(trans-stpyCOOMe)]+ complexes were obtained, R2phen = 1.10-phenanthroline 4,7-disubstituted and trans-stpyCOOMe = trans-4-(2-(4-pyridinyl)vinyl)methylbenzoate, which presents transcis and cistrans reversible photoisomerization. cis species are emissive and can be exploited in photosensors and photoswitches. The novel fac-[Re(CO)3(dcbH2)(trans-L)]+ complexes, dcbH2 = 4,4'-dicarboxy-2,2'-bipyridine and trans-L = trans-4-styrylpyridine (trans-stpy) or trans-1,2-bis (4-pyridyl)ethylene (trans-bpe), were strategically designed to show visible transcis photoisomerization under 436 nm irradiation for the first time, allowing application in energy conversion. In particular, the fac- [Re(CO)3(dcbH2)(trans-stpy)]+ complex also exhibited transcis photoreaction when adsorbed on the TiO2 surface, presenting good prospects in applications.
 
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Publishing Date
2021-11-30
 
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