Design and synthesis of organic-inorganic hybrid materials exhibiting optical and luminescent properties in the solid state

• Autores: Laura Jiménez García-Patron
• Directores de la Tesis: Ernesto Brunet Romero (dir. tes.)
• Lectura: En la Universidad Autónoma de Madrid ( España ) en 2012
• Idioma: inglés
• Tribunal Calificador de la Tesis: Carmen Carreño García (presid.), Bernardo Herradón García (secret.), Claude Forano (voc.), Muller Gilles (voc.), Aurelio Cabeza Díaz (voc.)
• Materias:
  • Química
• Enlaces
  • Tesis en acceso abierto en: Biblos-e Archivo
• Resumen

  • Design and synthesis of organic¿inorganic hybrid materials exhibiting optical and luminescent properties in the solid state Our modern society is mainly characterized by the use of new technologies. There is no new technology without the discovery of new materials. The design of porous solids, based in supramolecular structures, with properties that change when their wide enough cavities are accessed by external molecular species, is a challenge of great scientific and technological importance. Unfortunately, in the majority of cases the predictive knowledge of the structures or even the chemical composition of the solid materials is still a chimera. In contrast, the art or science of designing and synthesizing organic molecules has reached very high levels of sophistication, based upon a relatively simple set of rules that guide both the invention and synthesis of new compounds. As organic chemists confronted to the task of building new solid structures with tailored chemical properties, we do inevitably need to develop some rational approach and to establish the corresponding set of rules allowing for a realistic level of predictive knowledge in the construction of solid scaffolds.

    We found these conditions reasonably accomplished by the use of layered salts of tetravalent transition metals, namely zirconium phosphate, which are very versatile materials whose handling complies with what we have termed rational synthetic method, i.e. the development of a set of relatively simple rules that confers sufficient predictive knowledge to the building of crystalline materials. The synthetic rationale elaborated by us through a number of years is modular because it comprises the design and synthesis of appropriate organic molecules in one hand and on the other, their stepwise introduction into the inorganic framework. Specifically and directed to this aim, the ¿¿phase of zirconium phosphate (¿¿ZrP from now on) has been widely studied due to its thermal and chemical stability, its versatility and its unique property of replacing the superficial phosphates by phosphonates without affecting the integrity and rigidity of the inorganic layers. Furthermore, the structure of the lamellae of ¿¿ZrP is intrinsically dissymmetric as the internal phosphates bonded to four different Zr atoms are thus stereogenic centers.

    Results of our research group concerning the chemistry of metal phosphates/phosphonates in relation with recognition, chemically¿driven porosity changes, chiral memory and supramolecular chirality, luminescence signaling, photoinduced electron¿transfer, gas storage and drug confinement, led us to propose the following objectives for the development of this doctoral thesis: ¿ The design of supramolecular solid systems based on ¿¿ZrP which are capable of triggering efficient luminescence processes in order to perform the study of their photophysical properties in the solid state. Furthermore, due to the lack of a reliable methodology for quantifying the luminescence response, a protocol for determining the quantum yields in this kind of materials would be developed