. (2015). Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxide-functionalized metalorganic framework. CrystEngComm, 17 (46), 8858-8863.Thermally-promoted post-synthetic Pummerer chemistry in a sulfoxidefunctionalized metal-organic framework AbstractReported herein is a thermally-promoted, post-synthetic modification of a zinc metal-organic frameworks pore surface. Sulfoxide tag groups are modified by conventional heating via Pummerer-type chemistry and elimination to aldehyde groups. Simultaneously, a minor competing disproportionation reaction occurs, creating sulfide and sulfone tag groups enhancing the complexity of the pores. The thermal process is gentle, with crystallinity fully maintained, and results in a higher surface area and pore volume for the modified framework.
Subtleties of interpenetration are exposed and classified in the IRMOF-9 system.
. (2015). The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid. Dalton Transactions: an international journal of inorganic chemistry, 44 (19), 9269-9280.The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid AbstractThe synthesis, structural and thermal characterisation of a number of coordination complexes featuring the N,O-heteroditopic ligand 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoate, HL are reported. The reaction of H2L with cobalt(II) and nickel(II) nitrates at room temperature in basic DMF/H2O solution gave discrete mononuclear coordination complexes with the general formula {[M(HL)2(H2O)4]·2DMF} (M = Co (1), Ni (2)), whereas the reaction with zinc(II) nitrate gave [Zn(HL)2]∞, 3, a coordination polymer with distorted diamondoid topology and fourfold interpenetration. Coordination about the tetrahedral Zn(II) nodes in 3 are furnished by two pyrazolyl nitrogen atoms and two carboxylate oxygen atoms to give a mixed N2O2 donor set. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H2L and that of its protonated salt, H2L·HNO3, were also determined and revealed that H2L forms a 2-D hydrogen bonded polymer incorporating helical chains formed through N-HO and O-HN interactions, and that [H3L]NO3 forms a 1-D hydrogen-bonded polymer. The synthesis and characterisation of coordination and hydrogen-bonded networks based on 4-(3,5-dimethyl-1H-pyrazol-4-yl)benzoic acid donor sets with trans-square planar geometry and is fourfold interpenetrated. The desolvation of 8 was followed by powder X-ray diffraction and single crystal X-ray diffraction which show desolvation induces the transition to a more closely packed structure while the coordination geometry about the copper ions and the network topology is retained. Powder X-ray diffraction and microanalysis were used to characterise the bulk purity of the coordination materials 1-6 and 8. The thermal characteristics of 1-2, 4-6 and 8 were studied by TG-DTA. This led to the curious observation of small exothermic events in networks 4, 6, and 8 that appear to be linked to their decomposition. In addition, the solid state structures of H 2 L and that of its protonated salt, H 2 L•HNO 3 , were also determined and revealed that H
Reported here are the syntheses and adsorption properties of a series of single-and mixed-component zinc IRMOFs derived from controlled ratios of sulfide and sulfone functionalized linear biphenyldicarboxylate (bpdc) ligands. During MOF synthesis the sulfide moieties undergo in situ oxidation, giving rise to sulfoxide functionalized ligands, which are incorporated to give mixedcomponent sulfoxide−sulfone functionalized MOFs. The singleand mixed-component systems all share the IRMOF-9 structure type as determined by a combination of single crystal and powder X-ray diffraction analyses. The functionalized IRMOF-9 series was investigated by N 2 , CO 2 , and water adsorption measurements. MOFs containing higher proportions of sulfoxide have slightly larger accessible surface areas and pore volumes, whereas MOFs containing a greater proportion of the sulfone functionality demonstrated higher CO 2 adsorption capacities, enthalpies of CO 2 adsorption, and CO 2 /N 2 selectivities. Water adsorption studies at 298 K showed the MOFs to have pore-filling steps starting around 0.4 P/P 0 . In general, only small changes in water adsorption were observed with regards to ligand ratios in the mixed-component MOFs, suggesting that the location of the step is primarily determined by the pore size. A ligand-directed fine-tuning approach of changing alkyl chain length was demonstrated to give smaller more hydrophobic pores with better adsorption characteristics.
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