Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas
The present work is devoted to the synthesis and study of the properties of new heterometallic lead(II) and gold(I) complexes containing polydentate nitrogen donor molecules and perhalophenyl groups, respectively, as ligands. Their characterization has been carried out through the usual techniques,...
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Universidad de La Rioja (España)
2021
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The present work is devoted to the synthesis and study of the properties of new heterometallic lead(II) and gold(I) complexes containing polydentate nitrogen donor molecules and perhalophenyl groups, respectively, as ligands. Their characterization has been carried out through the usual techniques, in addition to through single crystal X-ray diffraction studies on a large number of cases. The crystal structures of these compounds have confirmed the presence of unsupported gold(I)·lead(II) interactions, very scarcely represented till the beginning of this work, in addition to aurophilic interactions in some cases. Theoretical studies on models based on the crystal structures have allowed us to analyze the relationship between the optical properties that these new derivatives present and their structures.
This dissertation is divided in three chapters:
The first chapter gathers the synthesis of heterometallic lead(II) and gold(I) compounds with different perhalophenyl groups (C6F5, 3,5-C6Cl2F3, C6Cl5, o-C6BrF4, o-C6F4I, p-C6BrF4 y p-C6F4I) bonded to the gold centers, as well as different donor nitrogen ligands (neocuproine, terpyridine and tetra-2-pyridinilpyrazine) coordinated to lead with the aim to analyze the possible influence of both types of ligands in the stoichiometry, structure and properties of the new derivatives synthesized, observing the formation of complexes of different nuclearity depending on the ligands employed, as well as the presence of different types of weak interactions as a function of the substituents in the aryl groups. Furthermore, a dependence of the optical properties, on which theoretical studies have been developed with the aim to understand their nature, on the ligands has been observed.
In the second chapter, a couple of derivatives with pentafluorophenyl and terpyridine groups bonded to gold and lead, respectively, have been designed and subsequently employed as if they were puzzle pieces to the controlled preparation of a decanuclear Au6Pb4 complex in which the building blocks are joined together through unsupported metallophilic interactions. Besides, one of these compounds exhibits a vapochromic reversible behavior against vapors of different small organic molecules, thus being a posible candidate to be employed as a volatile organic compounds (VOCs) sensor. In this chapter, the results obtained from the X-ray diffraction study at different pressures (between 0 and 2.1 GPa) carried out on some of the new derivatives in order to analyze the effect of this external factor in their crystal structures, and therefore, in their optical properties, merits a special mention. As in the previous chapter, theoretical studies that allow us to understand the origin of the emissive properties that these new complexes display are included.
The third and last chapter of this work is devoted to another type of supramolecular compounds, host-guest inclusion compounds. Thus, we were initially focused on the design and synthesis of trinuclear perhalophenyl gold(I) compounds with a tris(pyrazolyl)borate bridging ligand that can behave as organometallic host, studying the influence of the perhalophenyl groups bonded to gold in the size of the cavity of the host. Subsequently, these compounds were treated with a tris(pyrazolyl)borate lead complex likely to act as a guest, accommodating this compound within the host cavity, thus forming novel supramolecular host-guest complexes in which both parts are kept together thanks a series of weak interactions, among them standing out gold···lead contacts and non-conventional B-H·Pb hydrogen bonds. In addition, this chapter is completed with the theoretical study of the interactions present in this system to allow the encapsulation and accommodation of the guest molecule. |
| author2 |
López de Luzuriaga Fernández, José María (Universidad de La Rioja) |
| author_facet |
López de Luzuriaga Fernández, José María (Universidad de La Rioja) Moreno Infantes, Sonia |
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text (thesis) |
| author |
Moreno Infantes, Sonia |
| spellingShingle |
Moreno Infantes, Sonia Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| author_sort |
Moreno Infantes, Sonia |
| title |
Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| title_short |
Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| title_full |
Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| title_fullStr |
Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| title_full_unstemmed |
Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadas |
| title_sort |
estudio de nuevos sistemas supramoleculares basados en interacciones au(i)-pb(ii) no soportadas |
| publisher |
Universidad de La Rioja (España) |
| publishDate |
2021 |
| url |
https://dialnet.unirioja.es/servlet/oaites?codigo=293496 |
| work_keys_str_mv |
AT morenoinfantessonia estudiodenuevossistemassupramolecularesbasadoseninteraccionesauipbiinosoportadas |
| _version_ |
1718346698254712832 |
| spelling |
oai-TES00000230112021-11-06Estudio de nuevos sistemas supramoleculares basados en interacciones Au(I)-Pb(II) no soportadasMoreno Infantes, SoniaThe present work is devoted to the synthesis and study of the properties of new heterometallic lead(II) and gold(I) complexes containing polydentate nitrogen donor molecules and perhalophenyl groups, respectively, as ligands. Their characterization has been carried out through the usual techniques, in addition to through single crystal X-ray diffraction studies on a large number of cases. The crystal structures of these compounds have confirmed the presence of unsupported gold(I)·lead(II) interactions, very scarcely represented till the beginning of this work, in addition to aurophilic interactions in some cases. Theoretical studies on models based on the crystal structures have allowed us to analyze the relationship between the optical properties that these new derivatives present and their structures. This dissertation is divided in three chapters: The first chapter gathers the synthesis of heterometallic lead(II) and gold(I) compounds with different perhalophenyl groups (C6F5, 3,5-C6Cl2F3, C6Cl5, o-C6BrF4, o-C6F4I, p-C6BrF4 y p-C6F4I) bonded to the gold centers, as well as different donor nitrogen ligands (neocuproine, terpyridine and tetra-2-pyridinilpyrazine) coordinated to lead with the aim to analyze the possible influence of both types of ligands in the stoichiometry, structure and properties of the new derivatives synthesized, observing the formation of complexes of different nuclearity depending on the ligands employed, as well as the presence of different types of weak interactions as a function of the substituents in the aryl groups. Furthermore, a dependence of the optical properties, on which theoretical studies have been developed with the aim to understand their nature, on the ligands has been observed. In the second chapter, a couple of derivatives with pentafluorophenyl and terpyridine groups bonded to gold and lead, respectively, have been designed and subsequently employed as if they were puzzle pieces to the controlled preparation of a decanuclear Au6Pb4 complex in which the building blocks are joined together through unsupported metallophilic interactions. Besides, one of these compounds exhibits a vapochromic reversible behavior against vapors of different small organic molecules, thus being a posible candidate to be employed as a volatile organic compounds (VOCs) sensor. In this chapter, the results obtained from the X-ray diffraction study at different pressures (between 0 and 2.1 GPa) carried out on some of the new derivatives in order to analyze the effect of this external factor in their crystal structures, and therefore, in their optical properties, merits a special mention. As in the previous chapter, theoretical studies that allow us to understand the origin of the emissive properties that these new complexes display are included. The third and last chapter of this work is devoted to another type of supramolecular compounds, host-guest inclusion compounds. Thus, we were initially focused on the design and synthesis of trinuclear perhalophenyl gold(I) compounds with a tris(pyrazolyl)borate bridging ligand that can behave as organometallic host, studying the influence of the perhalophenyl groups bonded to gold in the size of the cavity of the host. Subsequently, these compounds were treated with a tris(pyrazolyl)borate lead complex likely to act as a guest, accommodating this compound within the host cavity, thus forming novel supramolecular host-guest complexes in which both parts are kept together thanks a series of weak interactions, among them standing out gold···lead contacts and non-conventional B-H·Pb hydrogen bonds. In addition, this chapter is completed with the theoretical study of the interactions present in this system to allow the encapsulation and accommodation of the guest molecule.El presente trabajo está dedicado a la síntesis y estudio de las propiedades de nuevos complejos heterometálicos de plomo(II) y oro(I) conteniendo compuestos nitrógeno dadores polidentados y grupos perhalofenilo, respectivamente, como ligandos. Su caracterización se ha llevado a cabo mediante las técnicas habituales, además de mediante estudios de difracción de rayos X sobre monocristal en un gran número de casos. Las estructuras cristalinas de estos compuestos han confirmado la presencia de interacciones oro(I)·plomo(II) no soportadas, muy poco representadas hasta el inicio de este trabajo, además de interacciones aurofílicas en algunos casos. Los estudios teóricos sobre modelos basados en las estructuras cristalinas nos han permitido analizar la relación entre las propiedades ópticas que presentan estos nuevos derivados y sus estructuras. La memoria se ha dividido en tres capítulos: El primer capítulo recoge la síntesis de compuestos heterometálicos de plomo(II) y oro(I) con diferentes grupos perhalofenilo (C6F5, 3,5-C6Cl2F3, C6Cl5, o-C6BrF4, o-C6F4I, p-C6BrF4 y p-C6F4I) unidos a los centros de oro, así como distintos ligandos nitrógeno dadores (neocuproína, terpiridina y tetra-2-piridinilpirazina) coordinados a plomo con objeto de analizar la posible influencia de ambos tipos de ligandos en la estequiometría, estructura y propiedades de los nuevos derivados sintetizados, observándose la formación de complejos de diferente nuclearidad dependiendo de los ligandos empleados, así como la presencia de distintos tipos de interacciones débiles en función de los sustituyentes de los grupos arilo. Además, se observa también una dependencia de los ligandos en las propiedades ópticas, sobre las cuales se han realizado estudios teóricos con objeto de entender la naturaleza de las mismas. En el segundo capítulo se han diseñado dos derivados con ligandos pentafluorofenilo y terpiridina unidos a oro y plomo, respectivamente, y posteriormente se han empleado como si se tratase de piezas de puzle para la preparación de forma controlada de un complejo decanuclear Au6Pb4 en el que los bloques de construcción se unen a través de interacciones metalofílicas no soportadas. Además, uno de estos compuestos presenta un comportamiento vapocrómico frente a vapores de diferentes moléculas orgánicas pequeñas de forma reversible, siendo un posible candidato para ser empleado como sensor de compuestos orgánicos volátiles (VOCs). En este capítulo merecen especial mención los resultados obtenidos del estudio de difracción de rayos X a diferentes presiones (entre 0 y 2.1 GPa) realizado sobre alguno de los nuevos derivados con objeto de analizar el efecto de este factor externo sobre su estructura cristalina y, por lo tanto, sobre sus propiedades ópticas. Como en el capítulo anterior, se incluyen estudios teóricos que permiten entender el origen de las propiedades emisivas que presentan estos nuevos complejos. El tercer y último capítulo de este trabajo se ha dedicado a otro tipo de compuestos supramoleculares, los compuestos de inclusión host-guest. Así, inicialmente nos centramos en el diseño y síntesis de perhalofenil compuestos trinucleares de oro(I) con un ligando tris(pirazolil)borato puente que puedan comportarse como anfitrión organometálico, estudiando la influencia de los grupos perhalofenilo unidos a oro en el tamaño de la cavidad del anfitrión. Posteriormente, se hicieron reaccionar estos compuestos con un tris(pirazolil)borato complejo de plomo(II) susceptible de actuar como huésped, alojándose éste en el interior de la cavidad del anfitrión formándose así novedosos compuestos supramoleculares host-guest en los que ambas partes se mantienen unidas a través de una serie de interacciones débiles, entre las que destacan los contactos oro···plomo y enlaces de hidrógeno no convencionales B-H·Pb. Además, este capítulo se completa con el estudio teórico de las interacciones presentes en estos sistemas para permitir la encapsulación y acomodación de la molécula huésped.Universidad de La Rioja (España)López de Luzuriaga Fernández, José María (Universidad de La Rioja)Olmos Pérez, María Elena (Universidad de La Rioja)2021text (thesis)application/pdfhttps://dialnet.unirioja.es/servlet/oaites?codigo=293496spaLICENCIA DE USO: Los documentos a texto completo incluidos en Dialnet son de acceso libre y propiedad de sus autores y/o editores. 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