Synthesis, structural characterization and functional properties of metal-organic frameworks based on poly(azolate) ligands.

In the firsts two Chapters, a brief introduction on the history of MOFs (Chapter 1), on the features of azolato- and poly(azolato)-based organic linkers and on the properties of fluorine and organofluorine compounds (Chapter 2) is exposed. In Chapter 3 the synthesis of six new non-fluorinated and fluorinated poly(pyrazolato)-, poly(tetrazolato)-, and tetrazolato-derivatives is described. Each linker has been designed for the specific application to be tested. In Chapter 4 the synthesis and characterization of a series of fluorinated and non fluorinated poly(pyrazolato)- poly(tetrazolato)-, and tetrazolato-based MOFs and N-PCPs are presented. The dielectric and CO2 adsorption properties of these new compounds have been investigated. In this context, the well known FMOF-1, has been successfully added to these compounds as a potential low- dielectric material. The synthesis and characterization of the first two Zn(II)-based MOFs ever used as molecular and dipolar rotors is presented in Chapter 5. The investigation on the rotational speed of their aromatic core has been performed with solid state NMR studies. Finally, using four known poly(pyrazolato)-based MOFs, we have tested their catalytic activity in the selective oxidation of hydroxymethylfurfural to diformylfuran. More important, we have disclosed the catalytic mechanism by means of DRIFT and in vacuo FT-IR spectroscopy. All the FT-IR measurements and catalytic results are discussed in Chapter 6.