$$\newcommand{\bra}[1]{\left<#1\right|}\newcommand{\ket}[1]{\left|#1\right>}\newcommand{\bk}[2]{\left<#1\middle|#2\right>}\newcommand{\bke}[3]{\left<#1\middle|#2\middle|#3\right>}$$
X
INFORMAÇÕES SOBRE DIREITOS AUTORAIS


As obras disponibilizadas nesta Biblioteca Digital foram publicadas sob expressa autorização dos respectivos autores, em conformidade com a Lei 9610/98.

A consulta aos textos, permitida por seus respectivos autores, é livre, bem como a impressão de trechos ou de um exemplar completo exclusivamente para uso próprio. Não são permitidas a impressão e a reprodução de obras completas com qualquer outra finalidade que não o uso próprio de quem imprime.

A reprodução de pequenos trechos, na forma de citações em trabalhos de terceiros que não o próprio autor do texto consultado,é permitida, na medida justificada para a compreeensão da citação e mediante a informação, junto à citação, do nome do autor do texto original, bem como da fonte da pesquisa.

A violação de direitos autorais é passível de sanções civis e penais.
Coleção Digital

Avançada


Estatísticas | Formato DC |



Título: ALDOL CONDENSATIONS AND CROSS-COUPLING ASSOCIATION AS A STRATEGY FOR OBTAINING PHOTOACTIVE AND BIOACTIVE COMPOUNDS
Autor: RAFAELA MARTINS DA COSTA VALEJO
Instituição: PONTIFÍCIA UNIVERSIDADE CATÓLICA DO RIO DE JANEIRO - PUC-RIO
Colaborador(es):  JONES LIMBERGER - ADVISOR
Nº do Conteudo: 60464
Catalogação:  05/09/2022 Idioma(s):  PORTUGUESE - BRAZIL
Tipo:  TEXT Subtipo:  THESIS
Natureza:  SCHOLARLY PUBLICATION
Nota:  Todos os dados constantes dos documentos são de inteira responsabilidade de seus autores. Os dados utilizados nas descrições dos documentos estão em conformidade com os sistemas da administração da PUC-Rio.
Referência [pt]:  https://www.maxwell.vrac.puc-rio.br/colecao.php?strSecao=resultado&nrSeq=60464@1
Referência [en]:  https://www.maxwell.vrac.puc-rio.br/colecao.php?strSecao=resultado&nrSeq=60464@2
Referência DOI:  https://doi.org/10.17771/PUCRio.acad.60464

Resumo:
It is possible to modulate the conjugated structures of the products, directing them to different applications from the association of aldol condensations and crosscouplings in known arylcarbonyl building blocks,. In this sense, this thesis is divided into four chapters concerning: (i) synthesis of analogues and hybrids of chalcones and BTDs; (ii) synthesis and application of chalcone-BTD hybrids as OLED devices; (iii) synthesis and evaluation of potential photosensitizers for DSSCs (dye-sensitized solar cells); (iv) synthesis of compounds with potential antiestrogenic activity. For the synthesis of all compounds, associations of aldol condensations and cross couplings were performed. Considering the recognized photophysical properties of chalcones and BTD derivatives, the synthesis of new photoactive BTD-chalcone hybrids is described. The products were obtained in two-step routes (Suzuki reaction and aldol condensation) and reaction yields ranged from 32 to 64 percent. The modulations in the structures were performed in such a way that the compounds were emissive in the aggregated state. Knowing the limitations of the development of luminescent films related to the aggregation-caused quenching effect(ACQ), compounds were synthesized with AIEE-like properties (aggregation-induced increased emission). The studies of its photophysical and electrochemical properties indicated that a compound with aryloxy-BTD-chalcone architecture presented the best results in which expressive increases were observed in fluorescence intensity (30x) and in fluorescence quantum yield (from 0.0070 to 0.143) with the aggregation. With these data, new analogs were synthesized respecting the aryloxy-BTD-chalcone (or -fluorene) with yields ranging from 42 to 79 percent. The new analogues also presented AIEE and were applied as emitting layers in bilayer structure OLEDs for evaluation and comparison of their electroluminescent performance. The association of cross-coupling and aldol condensation was also used as a strategy to produce new photosensitizers for DSSCs. To this end, D-pi-A-pi-A compounds were synthesized in which the terminal acceptor groups act as TiO2 anchors. The use of this type of structure facilitates the injection of electrons due to the directional transfer of electrons from the donor to the acceptor portion. Based on this, new derivatives of chalcones and BTDs were synthesized. The syntheses were performed in two steps resulting in yields of 35 to 44 percent. Electrochemical studies showed good HOMO, LUMO and band gap values for all compounds. The LUMO values were above the TiO2 semiconductor conduction range (-4.0 eV) which guarantees the necessary driving force for the directioning of electrons. In addition, the HOMO values of all compounds were lower than the redox potential of the electrolyte (-4.8 eV) generating a high driving force for dye regeneration. It was observed that the compounds absorb in a region close to 350 nm in different solvents, which makes their use as DSSCs difficult. Finally, in the last chapter, a new strategy was presented to obtain potentially bioactive molecules from the association between aldol condensations and coupling reactions. The alpha-beta unsaturated system of chalcone makes it an interesting platform for regio and stereoselective insertion of aryl substituents in the olefinic portion of the substrate. Based on a strategy of insertion of aryl moieties already described by our group, tamoxifen, a drug currently used in therapy for the treatment of some breast tumors, analogues were synthesized. Six products were synthesized via a Heck reaction, resulting in E/Z mixtures of approximately 50:50 and yields of 29 to 57 percent.

Descrição Arquivo
COMPLETE  PDF
Logo maxwell Agora você pode usar seu login do SAU no Maxwell!!
Fechar Janela



* Esqueceu a senha:
Senha SAU, clique aqui
Senha Maxwell, clique aqui