Nanoscale coordination polymers with molecular recognition. From nanocarriers and selective separations to 3d printing

Résumé

Coordination polymers are well-known compounds based on the self-assembly of metal ions and organic and inorganic ligands. However, the combination between metals and ligands is so versatile that not all the possibilities have already been studied. The use of nucleobases as ligands in combination with copper(II) as the metal ion is the thread of the work developed in the last four years, in which new potential biological, sensory, and analytical applications for coordination polymers have been described. The first chapter introduces the world of coordination polymers. Including a brief description of the evolution of these compounds from their first steps to current research, their design and principal obtention methods, their most characteristic properties, and some applications related to the following chapters. In Chapter 2, the synthesis at room temperature of a new nanoscale coordination polymer is described, including the process from single-crystal obtention in hydrothermal conditions to nanoscale the compound under mild conditions. Then the combination between the stable colloidal suspension, size, and properties of the synthesized coordination polymer with a thymine derivative as ligand allows its study as oligonucleotide carrier. Chapter 3 continues the study of the coordination polymer obtained in the previous chapter. The described synthesis of the nanoscale compound is transferred to a larger scale, enabling the use of this compound in the industry as ink for 3D printing. In addition, a deep study of the structure of the coordination polymer reveals its thermal and solvatochromic behavior. Indeed, the union of its properties with 3D printing allows us to create useful objects such as robust and simple water sensors. In Chapter 4, the rational design of two new coordination polymers to improve their cytotoxic activity in the biological media is reported. Two isostructural compounds are synthesized with nucleobase derivatives with the difference that one of them is also an analogue from an anticancer agent. Complementary studies of their behavior in biological media and their cytotoxicity are carried out. Finally, the last chapter introduces a new coordination polymer that is capable of changing from colloid to gel with a slight variation in the synthetic conditions. Later treatment of the gel enables to obtain new materials such as aerogel or a xerogel. The properties of the aerogel and the potential of the structure with a nucleobase derivate ligand are studied as a stationary phase of an HPLC column for selective methylated nucleobases separation.