Estudios estructurales, teóricos y de propiedades ópticas de nuevos compuestos con interacciones oro-mercurio stars

  1. David Pascual García
Supervised by:
  1. José María López de Luzuriaga Fernández Director
  2. María Elena Olmos Pérez Director

Defence university: Universidad de La Rioja

Year of defence: 2014

Committee:
  1. Antonio Laguna Castrillo Chair
  2. Laura Rodríguez Raurell Secretary
  3. Mario N. Berberan-Santos Committee member
Doctoral thesis with
  1. Mención internacional
Department:
  1. Chemistry

Type: Thesis

Teseo: 366939

Abstract

The present work is devoted to the synthesis of heterometallic compounds of mercury(II) with metals of group 11. The use of different mercury organometallic precursors with different coordinative and electronic capabilities has allowed us to synthesize and characterize a wide variety of compounds with metallophilic interactions by reaction with various compounds of gold(I), silver(I) and copper(I). This work has been divided in four sections according to the mercury(II) precursor employed in the reactions. The first chapter is focused on the synthesis of mercury(II) gold(I) heteronuclear derivatives using as precursors the neutral compounds [HgR2] (R = C6F5, C6Cl2F3) and [AuR(PR'3)] (R = C6F5, C6Cl2F3; R' = Me, Ph). In this section, the influence exerted by the ligands coordinated to the metals in the structural arrangements of the compounds is studied, as well as their photophysical properties and in the metallophilic interactions. This chapter also includes a theoretical study about the nature and strength of the metallophilic contacts present in the synthesized derivatives. In addition, we analyze how the different electronic capabilities of the ligands in these compounds affects, as well as their volume, in the ability to act as quenchers of the fluorescent emission of naphthalene. The study is completed by carrying out theoretical calculations that assist in understanding the origin of these processes. In chapter 2, we analyze the influence of the inclusion of nitrogen atoms, coordinatively unsaturated, both in the ligands bonded to the gold(I) metal centers as in those bonded to mercury(II), which allows for the analysis of the influence of the presence of a new heteroatom with free electron pair in the final derivatives, in its structure and in its properties as fluorescence quenchers, comparing the results with those of the previous chapter. Chapter 3 is dedicated to the preparation of new heterometallic compounds with metallophilic Hg(II)···Au(I) and Hg(II)···Au(III) interactions supported by the ligand 2?PPh2py as well as Hg(II) interactions with other metals of group 11 such as Ag(I) and Cu(I). This section includes a theoretical study that analyzes the strength of metallophilic interactions Hg···M (M = Au(I), Au(III), Cu(I), Ag(I)) present in the synthesized derivatives. In addition, an experimental study of the ability to quench the fluorescent emission of naphthalene in solution is carried out wherein both the influence of the heterometal and the structural arrangement of the derivatives are studied. The fourth and final chapter of this thesis concerns the synthesis and characterization of heterometallic ionic cyclic gold(I) and mercury(II) compounds. We studied their ability to act as quenchers of the emission in solution of different fluorophores such as naphthalene, biphenyl or pyrene. Finally, the realization of a theoretical study has allowed a deeper analysis of the metallophilic interactions present in these species.