Stimuli-responsive subphthalocyanine- and anthracene-based multicyano systems: Structural, electrochemical andphotophysical properties

• Autores: Oscar Fernández Vera
• Directores de la Tesis: Giovanni Bottari (dir. tes.), Tomás Torres Cebada (dir. tes.)
• Lectura: En la Universidad Autónoma de Madrid ( España ) en 2024
• Idioma: inglés
• Número de páginas: 363
• Títulos paralelos:
  • Sistemas multiciano basados en subftalocianina y antraceno que responden a estímulos: Propiedades estructurales, electroquímicas y fotofísicas
• Enlaces
  • Tesis en acceso abierto en: Biblos-e Archivo
• Resumen

  • This Thesis is focused on two main objectives. On the one hand, the preparation and study of subphthalocyanines (SubPcs), either monomeric functionalised in their axial position by extended tetracyanoquinodimethane (extTCNQ) units or dimeric functionalised in their axial position by (tetracyanobutadiene) TCBD units. On the other hand, the synthesis of molecular systems based on anthracenes or anthracene-SubPc systems functionalised by TCBD or extTCNQ has been addressed, followed by the study of the transformation of these tetracyano units by intramolecular cyano Diels-Alder (CDA) reactions with the anthracene fragment. In the first Chapter, the preparation of two functionalized SubPcs is reported, bearing in their peripheral position hydrogen or fluorine atoms, and in their axial position an extTCNQ-dimethylaniline unit, using a cycloaddition-retroelectrocyclization (CA-RE) reaction between TCNQ and SubPc-ethynyl-dimethylaniline. Prior to this thesis, studies had shown that SubPcs functionalised in their axial position by a TCBD-dimethylaniline group could be separated into their enantiomers by chiral high-performance liquidi chromatography (HPLC). In addition, the racemization of these enantiomers under different stimuli had been explored, showing that this process required light (photoracemisation) and the absence of oxygen. Furthermore, it was decided to prepare SubPc-extTCNQ analogues and to study the possible separation of racemic mixtures of SubPc-extTCNQ-dimethylaniline into their enantiomers, as well as the racemisation of these derivatives, comparing them with the SubPc-TCBD-dimethylaniline systems studied previously. It was also intended to investigate the possible CA-RE reaction between a SubPc dimer, obtained as a by-product in the preparation of a precursor of F12SubPc-ethynyl-dimethylaniline, and TCBD or TCNQ. The second objective, developed in Chapter 2, focuses on the preparation of new anthracene-based derivatives functionalised by extTCNQ units. Previous studies had shown that anthracene derivatives substituted at position 9 by a TCBD unit could undergo an intramolecular CDA reaction, generating a fused product with intriguing structural and optoelectronic properties. In this second chapter, we aim to investigate the CA-RE reaction between ethynyl-dimethylaniline groups at different positions of an anthracene substrate and TCNQ, as well as the transformation of the resulting anthracene-extTCNQ-dimethylaniline derivatives by intramolecular CDA reactions. It is proposed to isolate both the "open" anthracene-extTCNQ adduct and its "fused" analogue, studying the differences in their physicochemical properties. In addition, in this second Chapter, we aim to prepare a SubPc functionalized at its peripheral position by multiple anthracene-ethynyl-dimethylaniline units, with the objective of studying the functionalization of this system by TCBD or extTCNQ units, as well as possible intramolecular CDA reactions, with the ultimate objective of comparing the physicochemical properties of SubPc systems without and with functionalization by tetracyano units, exploring the effect of intramolecular fusion of the tetracyano unit to the anthracene through intramolecular CDA reactions