Porous organic and hybrid materials based on tailor-made singular units: Synthesis and applications

• Autores: Antonio Valverde González
• Directores de la Tesis: Marta Iglesias Hernández (dir. tes.), Avelina Arnanz Lara (dir. tes.)
• Lectura: En la Universidad Autónoma de Madrid ( España ) en 2022
• Idioma: inglés
• Número de páginas: 196
• Tribunal Calificador de la Tesis: Rosa María Martín Aranda (presid.), Ana Eva Platero Prats (secret.), Matthieu Raynal (voc.)
• Programa de doctorado: Programa de Doctorado en Química Aplicada por la Universidad Autónoma de Madrid
• Materias:
  • Física
    • Química física
      • Cinética química
      • Química del estado sólido
    • Termodinámica
  • Química
    • Química inorgánica
    • Química orgánica
• Enlaces
  • Tesis en acceso abierto en: Biblos-e Archivo
• Resumen

  • In this doctoral thesis a catalytic study of several porous materials is presented. These obtained materials can be divided in two big groups: non-chiral materials and binaphthyl-based chiral materials. These materials are insoluble solids due to the 3D hypercrosslinked networks formed. Indeed, it its complete insolubility and high porosity the raison why these materials have been widely employed like heterogeneous catalysts, and whenever a chiral moiety is present in the structure, in asymmetric heterogeneous catalysis.

    The most representative results obtained are: “Knitting Aryl Polymers” (KAPs) One of the different materials prepared are the so-called metal-“Knitting Aryl Polymers”, also known as metal-KAPs. They belong to the bigger group of POPs (Porous Organic Polymers) firstly reported in 2011 and they are based on the typical Friedel-Crafts reaction. Our group, was one of the first to report the polymerization of coordination complexes, rather than by post-functionalization of purely organic KAPs. In 2021, a literature review about these types of metal-KAPs, and more generally about porous materials, was reported by our group, being focus in heterogenous catalysts.

    Metal Catalysis with Knitting Aryl Polymers: Design, Catalytic Applications, and Future Trends. Antonio Valverde-González, Marta Iglesias, and Eva M. Maya. Chem. Mater. 2021, 33, 17, 6616–6639 A step forward in solvent knitting strategies: ruthenium and gold phosphine complex polymerization results in effective heterogenized catalysts Antonio Valverde-González, Gwendoline Marchal, Eva M. Maya and Marta Iglesias Catalysis Science & Technology 2019, 9, 4552 Iron Phthalocyanine-Knitted Polymers as Electrocatalysts for the Oxygen Reduction Reaction Antonio Valverde-González, Li Zhi Guan, M. Luisa Ferrer, Marta Iglesias, and Eva M. Maya. ACS Appl. Mater. Interfaces 2020, 12, 29, 32681–32688 “Metal-Organic Frameworks” (MOFs) A second family of materials prepared are the metal-organic frameworks (MOFs). They were firstly reported in the 90’s, and its extremely unexpected high porosity, higher than zeolites, was such a breakthrough in material’s chemistry. Typically, MOFs have been prepared by combining carboxylic acids and a metallic ion, forming the so-called secondary building units, SBU), which along with the ligand geometry define the MOF’s topology. Herein we have employed tetrazole-based ligands, instead of carboxylic acid, its multiple coordination modes enable the formation of different topologies. Cobalt and nickel have been employed to construct the MOFs.

    The manuscript with all these results is now under preparation: Naphthalene tetrazol-based MOFs for the tandem olefin epoxidation and CO2 cycloaddition reactions.

    Chiral Binaphthyl Porous Polymers Lastly, the third family of materials are chiral porous polymers, 1,1’-binaphthol and binaphthyl-dihydro-azepine are being employed as building block. These polymers have been prepared by carbon-carbon couplings like Suzuki and Sonogahsira.

    Binaphthol-based materials have been studied as fluorescent sensors, due to the fact that fluorescence emission mainly decrease in presence of one enantiomer of the terpenes analytes: α-limonenoe o el α-pinene. Furthermore, they have also been used as chiral catalysts for the titanium catalysed diethylzinc addition to aldehydes.

    The binaphthyl-dihydro-azepines material have been widely studies as heterogeneous chiral catalyst, both in organometallic and organocatalytic conditions, in the diethylzinc addition to aldehydes, the copper catalysed nitromethane addition to aldehydes, the A3 multicomponent reaction and the Mannich reaction with nitro styrene. These results are now being prepared in two different manuscript Chiral Porous Polymers Based on BINOL Building Blocks for Enantioselective Fluorescence Sensing with Total Enantiodescrimination.

    Unveiling the gap between the heterogeneous and homogeneous nature of with binaphthyl-dihydro-azepines materials: A chiral catalytic and sensing study