Design And Regioselective SynThesis Of Fullerene Derivatives For Metal-Organic Hybrid Architectures

In the last years different fullerene derivatives and endohedral fullerenes have been reported and their potential applications as electronic, magnetic, catalytic, biological and optical materials have been explored. In this work we describe the characterization of new endohedral fullerenes; the exohedral functionalization of fullerenes with organic addends or metal clusters and their application in metal-organic hybrid architectures. We synthesized fullerene polymers with a variety of staircase linear architectures, zigzag polymers and a perfectly linear polymer using an hexakis-fullerene adduct with two 4,5-diazafluorene groups located at trans-1 positions, using Hg, Cd, Zn and33 Cu as the metal centers. Our results showed that both, the metal and the metal:ligand ratio, have an impact on the structural and optical properties of the polymeric chains. To date, there are no reports of a 3D porous-metal organic framework (MOF) where fullerenes are used as integral linkers of the structure as opposed to adsorbed inside the pores. We designed, synthesized and characterized different carboxylate-fullerene derivatives to be used as integral linkers in MOFs. Furthermore, we explored the construction of fullerene based bimetallic units; we synthesized a discrete molecular system using dimolybdenum units and a carboxylate fullerene derivative. Of particular interest is the electronic coupling between the metallic center and the fullerene cage. For the synThesis of the carboxylate fullerene derivative we explored an unprecedented synthetic methodology for 1,3-dipolar cycloaddition reactions. We also purified and characterized an endohedral fullerene with formula Lu2C82. Our results indicate that Lu2C82 corresponds to the dimetallic endohedral Lu2@C82 and not to the corresponding carbide Lu2C2@C80. The dimetallic endohedral was characterized by MALDI-TOF MS, UV spectrometry and electrochemistry. Finally, we synthesized the first bis-parallel C60-metal cluster complex: parallel-[Ru3(CO)9]2{μ3-η2,η2,η2-C60[C(COOC2H5)2]4}