Perovskite-based nanohybrids: synthesis and photophysics

• Autores: Alejandro Cortés Villena
• Directores de la Tesis: Julia Pérez Prieto (dir. tes.), Raquel Eugenia Galian (codir. tes.)
• Lectura: En la Universitat de València ( España ) en 2025
• Idioma: español
• Tribunal Calificador de la Tesis: Felix N. Castellano (presid.), Virginia Martínez Martinez (secret.), Alejandro Cadranel (voc.)
• Programa de doctorado: Programa de Doctorado en Química Sostenible por la Universidad de Castilla-La Mancha; la Universidad de Extremadura; la Universidad Jaume I de Castellón; la Universitat de València (Estudi General) y la Universitat Politècnica de València
• Materias:
  • Física
    • Química física
      • Fotoquímica
• Enlaces
  • Tesis en acceso abierto en: TESEO
• Resumen

  • This thesis explores energy transfer (ET) mechanisms at the interface in perovskite-based nanohybrids functionalized with various dye molecules. We systematically demonstrated how quantum confinement and surface chemistry of CsPbBr3 nanocrystals (NCs) influence the energy transfer efficiency to surface-anchored BODIPY dyes. Smaller NCs favored the Förster resonance energy transfer (FRET), while larger NCs exhibited charge transfer (CT) as the dominant nonradiative pathway. Using a BODIPY molecular rotor, we tracked dye localization while no impact on the ET efficiency, highlighting the critical role of surface ligands. We also assessed two nanohybrids, NC@BDP and NC@I2-BDP, showing completely distinct ET mechanisms influenced by iodine substituents, achieving singlet oxygen generation via triplet energy transfer (TET), and demonstrating oxidative photocatalytic activity of the NC@I2-BDP as a proof-of-concept. Additionally, we uncovered an unusual, concerted Dexter-type energy transfer (DET) mechanism in perovskite-phthalocyanine (NC@ZnPc) nanohybrids, where NC surface chemistry controlled dye aggregation and extended triplet state lifetimes, offering potential for singlet oxygen-mediated photocatalytic applications. Then, novel linear and co-assemblies of upconversion nanoparticles (UCNPs) and CsPbX3 (X: Br, I) NCs were also successfully prepared, demonstrating near-infrared (NIR) harvesting and efficient lanthanide resonance energy transfer (LRET) mechanism under NIR excitation, suggesting potential use in photovoltaic applications. Lastly, we analyzed the relaxation pathways in biphenyl derivatives, focusing on push-pull systems with electron-donating amino groups and electron-accepting pyrimidine moieties. This study showed how molecular structure and solvent environments significantly affect their optical and photophysical properties. Collectively, these findings advance the development of light-harvesting and photocatalytic systems, opening new possibilities for solar energy conversion and sustainable chemical synthesis, contributing to solutions for global energy and environmental challenges.