Rotaxanos de amidas bencílicasestudio de la conmutación del movimiento de sus componentes y su organización en sistemas metal-orgánicos

Resumo

Abstract The research on synthetic molecular machines is still in its early stages. Most of the prepared systems are relatively basic, including molecular switches or rotors. Considering the existing background on molecules with mechanically interlocked components, amide-based rotaxanes have emerged as suitable candidates for the development of nanoscale machines. In this type of rotaxanes, the components are connected through hydrogen bonds. This project aims to develop new approaches and methodologies to control the rotational and translational motion of the intercomponents of rotaxanes, through reversible manipulation of hydrogen bonding interactions or through simple chemical modifications. In addition, this Doctoral Thesis seeks to advance the research already carried out in the research group through the organization of these intertwined systems in metal-organic structures. The Doctoral Thesis is divided as follows: Chapter 1 is an introduction to the general concepts of rotaxanes, as well as the current state of the research field of this type of molecules. In Chapter 2, the synthesis of novel azo- and hydrazodicarboxamide-based [2]rotaxanes, decorated with pyridine motifs in the macrocycle, is described. Through the azo/hydrazo interconversion, the switching in the circumrotation rate was evaluated as a function of the binding site oxidation level. In Chapter 3, the synthesis of a series of fumaramide-based [1]rotaxanes is described. The fumaramide/maleamide photoisomerization was investigated as the driving force enabled to control the interconversion between the extended and contracted forms of the synthesized [1]rotaxanes. In Chapter 4, the employment of a new template based on a thiodiglycolamide station is evaluated for the formation of molecular shuttles. These systems operate as photoswitchable catalysts. In Chapter 5, the preparation of a photoresponsive copper metal-organic framework with fumaramide-based [2]rotaxanes as organic ligands is described. The capacity of these metal-organic systems as p-benzoquinone dosing containers was evaluated. In Chapter 6, the preparation of copper(II) and zinc(II)-based metal-organic frameworks bearing carboxylic acid-based macrocycles as organic ligands is described. These metalopolymers were used for the selective recognition of fullerene derivatives. In Chapter 7, the general conclusions of the Thesis are described.