El pirazol com a plataforma pel disseny de lligands: síntesi de nous lligands i compostos de coordinació
- Autores: Joan Soldevila Sanmartin
- Directores de la Tesis: José Giner Planas (dir. tes.), Josefina Pons Picart (codir. tes.)
- Lectura: En la Universitat Autònoma de Barcelona ( España ) en 2021
- Idioma: catalán
- Tribunal Calificador de la Tesis: María Concepción López Martínez (presid.), Jordi García-Antón Aviñó (secret.), María Isabel Romero García (voc.)
- Programa de doctorado: Programa de Doctorado en Química por la Universidad Autónoma de Barcelona
- Materias:
- Enlaces
- Tesis en acceso abierto en: TDX
- Resumen
This PhD mainly revolves about the synthesis of pyrazole-derived ligands and their coordination compounds. The particular ligands used in this work are tri-substituted pyrazole rings (positions 1- (N-substitution), 3- and 5-), which can be classified in three families: N-hydroxyethylpyrazole, bispyrazole ether and N-alkylcarborane ligands. In this work, six previously unreported ligands have been synthesized for the first time, and thirty-two metal complexes have been obtained.
Chapter 1 starts by offering an overview of the Design of Metal Organic Materials (DMOM) group past work in the synthesis of pyrazole-derived ligands as well as in the background of the Laboratory of Inorganic Materials and Catalyst’s (LMI) group in incorporating N-heterocycles to the carborane moiety.
Chapter 2 states the general and specific objectives for this thesis.
Chapter 3, where the results obtained during this work are discussed, is divided in five sections: Section 3.1 contains the synthesis and characterization of six new pyrazole derived ligands. The first three (L6-L8) belong to the bispyrazole ether family, and incorporate phenyl moieties in positions 3- and 5-. The next three (L9-L11) are the first examples of N-alkylcarborane pyrazole ligands.
Section 3.2 describes the reactivity of a family of three different N-hydroxyethylpyrazole ligands bearing methyl, phenyl or 2-pyrydil groups (HL1-HL3) against different Cu(II) salts. The crystal structures of the nine resulting compounds have been elucidated, allowing the study of their molecular structures and supramolecular networks. These studies lead to the assessment that the alcohol moiety is the key player in determining the nuclearity of the resulting compounds.
Section 3.3 focuses on bispyrazole ether ligands. In the first part, the reactivity of two positional isomers of a bispyrazole ligand (L4 and L5) against different MCl2 salts (M = Zn(II), Cd(II), Hg(II), Co(II) and Cu(II)) has been assayed. This afforded ten coordination compounds bearing three clearly different topological motifs: dimeric metallacycles for L4, and 1D polymers and dimers for L5, demonstrating the effect of the relative position of the pyrazole arms in the topology of the resulting compounds. In the second part, the reactivity of the novel ligands L6-L8 against Pd(II) is assayed, and the results compared with those previously obtained with L4 and L5.
In Section 3.4, the first coordination complexes containing N-alkylcarborane pyrazole ligands are described. In this work, a total of six coordination compound bearing L9-L11 and different metal centres (Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II)) are described, allowing the observation of the effect of adding the carborane moiety to the pyrazole backbone.
Section 3.5 describes the obtention of four luminescent Cu(I) compounds bearing ligands L9-L12. Some of them bear particularly rare motifs, and their obtention during the same work is remarkable. Moreover, the study of their luminescent behaviour has allowed us to investigate the emission processes in some scarcely studied compounds. These studies are backed by TDDFT calculations.
In Chapter 4 the general conclusions of this work are presented.
Moreover, for the sake of completeness, this work also contains and experimental section (Chapter 5) and an annex (Annex I) which contains all the spectra and additional information for this work.
Finally, all the related publications for this work can be found in Annex II
