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Doctoral Thesis
DOI
https://doi.org/10.11606/T.59.2020.tde-11082020-150415
Document
Author
Full name
Renato Salviato Cicolani
Institute/School/College
Knowledge Area
Date of Defense
Published
Ribeirão Preto, 2020
Supervisor
Committee
Demets, Gregoire Jean Francois (President)
Alves Junior, Severino
Araki, Koiti
Nikolaou, Sofia
Oliveira, Kleber Thiago de
Pastore, Heloise de Oliveira
Title in Portuguese
Sobre compostos de metil-bambus[6]urila com halogênios e terras-raras
Keywords in Portuguese
Adutos
Bambusurilas
Halogênios
Terras-raras
Trihaletos
Abstract in Portuguese
Nessa tese, apresentamos alguns compostos de inclusão de metil-bambusurila (MeBU[6]) com halogênios (iodo, bromo e brometo de iodo), além de um estudo sobre compostos de íons terras-raras(III) (ítrio, lantânio, cério, praseodímio e európio) com esse mesmo macrociclo. Com relação aos compostos de MeBU[6] com halogênios gasosos, verificamos que o macrociclo contendo íon cloreto caviplexado é capaz de capturar maiores quantidades de gases iodo, bromo e brometo de iodo que a MeBU[6] sem ânion. Ao longo da pesquisa, descobrimos que o íon cloreto interage diretamente com os halogênios supracitados e por conta disso a capacidade de adsorção do caviplexo de MeBU[6] contendo íon cloreto é maior. Além disso, aplicamos os caviplexos de MeBU[6] com iodo, bromo e brometo de iodo como fonte de halogênios para algumas reações orgânicas clássicas e concluímos que esses compostos podem ser utilizados ao invés dos halogênios livres, com a principal vantagem de um manuseio mais prático. No caso dos compostos de MeBU[6] com os íons trivalentes ítrio, lantânio, cério, praseodímio e európio, obtivemos produtos sólidos por vias solvotermais. Após a caracterização, concluímos que os compostos obtidos não se tratavam de complexos de coordenação, mas sim adutos de MeBU[6] com complexos dos íons terras-raras(III) contendo água como ligante. Utilizando o íon európio(III) como sonda estrutural, pudemos concluir que esse cátion estava inserido em um ambiente de baixa simetria no composto e que o aduto era facilmente dissociado em soluções aquosas. O mesmo raciocínio foi expandido para os demais adutos por conta da similaridade química de íons terras-raras(III).
Title in English
On methyl-bambus[6]uril compounds with halogens and rare-earths
Keywords in English
Adducts
Bambusurils
Halogens
Rare earths
Trihalides
Abstract in English
In this thesis, we present some compounds of methyl-bambus[6]uril (MeBU[6]) with halogens (iodine, bromine and iodine bromide) and rare earth ions(III) (yttrium, lanthanum, cerium, praseodymium and europium). Regarding the methyl-bambus[6]uril compounds with gaseous halogens, we have found that the chloride-bearing macrocycle captures greater amounts of iodine, bromine and iodine bromide gases than the anion-free methyl-bambus[6]uril. Throughout the research, we found that chloride ions interact directly with the halogens and increase the adsorption capacity of chloride-bearing methylbambus[6]uril. In addition, we applied the methyl-bambus[6]uril caviplexes with iodine, bromine and iodine bromide as a source of halogens for some classical organic reactions and have concluded that these compounds can be used instead of free-halogens, with the advantage of being more practical to handle. In the case of methyl-bambus[6]uril compounds with the trivalent ions yttrium, lanthanum, cerium, praseodymium and europium, we obtained solid products using solvothermal methods. After characterization, we concluded that compounds were adducts of methyl-bambus[6]uril with water-rare earth(III) complexes, instead of methyl-bambus[6]uril coordination compounds. By using the europium(III) ion as a structural probe, we concluded that the cation was inserted in a low-symmetry region in the compound and that the adduct was easily dissociated in aqueous solutions. The same logic was applied to the other adducts due to the rare-earth ions(III) chemical similarity.
 
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Publishing Date
2020-11-19
 
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