Ligandos metálicos trispiridilo de aluminio, antimonio y bismuto: efecto del átomo puente en su reactividad y ensamblaje supramolecular

The work collected in this PhD thesis encompasses the synthesis, characterization, coordination chemistry, and reactivity of a series of trispyridyl compounds of metallic main-group elements of groups 13 and 15, concretely, aluminium, antimony and bismuth, and their use as building blocks in supramo...

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Detalles Bibliográficos
Autor: García Romero, Álvaro
Tipo de recurso: tesis doctoral
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Valladolid
Repositorio:UVaDOC. Repositorio Documental de la Universidad de Valladolid
OAI Identifier:oai:uvadoc.uva.es:10324/59751
Acceso en línea:https://doi.org/10.35376/10324/59751
https://uvadoc.uva.es/handle/10324/59751
Access Level:acceso abierto
Palabra clave:Química inórganica
Supramolecular chemistry
Organometallic
Organometálica
Supramolecular
Inorganic Chemistry
Síntesis Química
2303 Química Inorgánica
Descripción
Sumario:The work collected in this PhD thesis encompasses the synthesis, characterization, coordination chemistry, and reactivity of a series of trispyridyl compounds of metallic main-group elements of groups 13 and 15, concretely, aluminium, antimony and bismuth, and their use as building blocks in supramolecular chemistry. The results of this work have been divided into three chapters: Chapter I describes (i) a post-functionalization strategy for tris(2-pyridyl) aluminates via their reaction with alcohols, which allows the introduction of chirality into the aluminate and access to supramolecular chemistry by introducing functionalities in the form of alkoxy groups, and (ii) the synthesis of the first anionic derivative of the tris(3-pyridyl) family of compounds and its unusual stability due to the absence of cooperativity between the aluminium and lithium metal centers. Chapter II reports (i) the modulation of the anion- and cation-coordinating ability of a family of tris(2-pyridyl)bismuthines through the introduction of substituents on the pyridinic rings, as well as their non-innocent reactivity, and (ii) the synthesis of tris(3-pyridyl) ligands of antimony and bismuth and the directing effect of the bridgehead atom in the construction of supramolecular structures by ligand coordination to metal centers. Finally, Chapter III presents the formation of supramolecular capsules based on the coordination of the tris(3-pyridyl) ligands of antimony and bismuth to metalloporphyrins. The different geometric profiles of the ligands, as well as the oxidation of the bridgehead atom, can be used to modulate the dimensions, morphology and dynamic behavior of the capsules.