Enhancing metal-organic framework net robustness by successive linker coordination increase: from a hydrogen-bonded two-dimensional supramolecular net to a covalent one keeping the topology

This work is to emphasize the influence of the synthetic procedures in the isolation of different coordination polymers (CPs) that coexist under hydrothermal conditions, and to determine, both experimental and theoretically, the driving forces that govern the reaction in the YbIII/3,5-DSB/Phen system, to give the following Yb-metal-organic frameworks (MOFs): [Yb(3,5-DSB)(Phen)2(H2O)2]·(H2O)1/2(RPF-20-initial) in which all the reactant are stoichiometrically incorporated into the compound; the one-dimensional [Yb(3,5-DSB)(Phen)(H2O)2]·H2O,(RPF-20-prec), in whose structure hydrogen bonds built up a SP 2-periodic (6,3) Ia supramolecular net; the covalent two-dimensional (2D) [Yb(3,5-DSB)(Phen)(H2O)]·H2O, (RPF-20-Yb), with exactly the same (6,3) Ia net topology as its precursor; and the [Yb(3,5-DSB)(Phen)2(OH)3(H2O)], (RPF-24-Yb) built up from tetranuclear Yb4O14N8secondary building units. Computational studies have determined the relative energies for the formation of four successively obtained compounds. From the crystallographic (structural and topological) study it is also shown, that it is possible to go from a hydrogen bonded 2D supramolecular net to the covalent one, keeping the topology.R.D. acknowledges a FPI scholarship from Spanish Ministry of Science and Innovation (MICIN), and Fondo Social Europeo from the EU, and a CAPES/PNPD scholarship from Brazilian Ministry of Education and Crystallography Group from IFSC-USP. This work has been supported by the Spanish MCYT Project MAT2010-17571, MAT2014-, Consolider-Ingenio CSD2006-2010, PHAMA S2009/MAT-1756 Comunidad Autónoma de Madrid