A series of new Ti(IV)-oxo clusters supported by carboxylate ligands are synthesized by solvothermal reactions, and their crystal structures and gas sorption properties are studied in detail. Depending on the reaction medium, two types of Ti6O6 clusters are formed with benzoate-derived ligands whose 2- or 4-position is substituted by a hydrophobic moiety. The molecular packing structures of these Ti clusters are found stable against water- and heat-treatments. Gas sorption studies reveal that a dense-packed Ti-carboxylate cluster can adsorb almost the same number of CO2 molecules as the one with considerable intermolecular voids in the packing structure. The effect of benzoate substituents on the gas sorption behavior is discussed.
A heterometallic metal-organic framework incorporating Zn(2+) and Ti(4+) is successfully synthesized. The unique coordination mode of each metal ion to 2-oxido-1,4-benzenedicarboxylate leads to Zn6Ti2 building blocks, which extend to form a double-walled primitive cubic net. This material possesses a permanent porosity and long-term stability.
A facile method to transform metal-organic frameworks (MOFs) into metal/metal oxide@carbon (M/MO@C) composites with well-defined shapes is reported. The porosity of carbon and the particle sizes of M/MO are readily controlled by a simple two-step process that includes impregnation of the polymer precursors and a thermolysis reaction.
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