A mixed-valence uranium oxide hydrate framework with Sr2+ ions (UOF-Sr2) was synthesized hydrothermally and characterized with multiple structural and spectroscopic techniques. Compound UOF-Sr2 crystallizes in monoclinic space group C2/c, having...

Two new mixed-valence uranium oxide hydrate frameworks (UOFs), incorporating either Er3+ or Y3+ ions, were successfully synthesised under hydrothermal conditions and characterised with single-crystal X-ray diffraction and a variety of...

. (2016). High temperature postsynthetic rearrangement of dimethylthiocarbamate-functionalized metal-organic frameworks. Crystal Growth and Design, 16 (12),[7067][7068][7069][7070][7071][7072][7073] High temperature postsynthetic rearrangement of dimethylthiocarbamatefunctionalized metal-organic frameworks AbstractA thermally promoted postsynthetic rearrangement has been performed on a zinc IRMOF-9-type framework bearing dimethylthiocarbamate tag groups. The rearrangement was accomplished via conventional heating at 285 °C. Crucially, despite the high temperature, the MOF maintains its high accessible surface area and pore space following thermal treatment. The structures and physical properties of the frameworks were characterized by a combination of single-crystal X-ray diffraction, powder X-ray diffraction, differential thermal-thermogravimetric analysis, and gas sorption analysis. The rearrangement results in a slightly higher level of CO 2 adsorption for the modified MOF but with equivalent heat of adsorption. This work offers new perspectives on postsynthetic rearrangements in MOFs and demonstrates that rearrangements that occur at relatively high temperatures are still compatible with the need to retain the structural integrity and porosity of the framework. A thermally-promoted post-synthetic rearrangement has been performed on a zinc IRMOF-9 type framework bearing dimethylthiocarbamate tag groups. The rearrangement was accomplished via conventional heating at 285 °C. Crucially, despite the high temperature, the MOF maintains its high accessible surface area and pore space following thermal treatment. The structures and physical properties of the frameworks were characterized by a combination of single X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), differential thermalthermogravimetric analysis (DT-TGA), and gas sorption analysis. The rearrangement results in a slightly higher level of CO 2 adsorption for the modified MOF but with equivalent heat of 2 adsorption. This work offers new perspectives on post-synthetic rearrangements in MOFs, and demonstrates that rearrangements that occur at relatively high temperatures are still compatible with the need to retain the structural integrity and porosity of the framework.

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Direct radiative heating at 200 °C quantitatively converts sulfoxide-tags to desirable vinyl groups on a porous zinc(ii) metal–organic framework analogue of IRMOF-9.

We report the synthesis of two new dual-cation uranium oxide hydrate (UOH) materials, containing both Cd2+ and K+ ions, along with their characterisation by means of single-crystal X-ray diffraction and...

Herein, we report coupling in situ high temperature postsynthetic modifications (PSMs) in metal–organic frameworks (MOFs). Thermo-reactive propargyloxy-functionalized zinc IRMOFs (isoreticular metal–organic frameworks) prepared from 2-(prop-2-yn-1-yloxy)-[1,1′-biphenyl]-4,4′-dicarboxylic acid (H2bpdcOCH2CCH) were investigated for their high-temperature postsynthetic rearrangement (PSR) chemistry to heterocyclic chromenes and benzofurans and then coupled to solid–gas reactions with molecular oxygen. The selectivity for the initial molecular rearrangements was found to be inverted in the porous MOF environment compared to conventional melt reactions of the ester compound Me2bpdcOCH2CCH and proceeded far more easily than the solid-state transformation from H2bpdcOCH2CCH, showing the potential of MOFs to give rise to different chemistry. The major oxidative process was thermolysis of the chromene ring with a minor pathway of allylic-type oxidation to give heterocyclic chromenone functionality. The sequence was also successful on a series of two-component multivariate IRMOF frameworks prepared from thermo-reactive H2bpdcOCH2CCH and thermo-resistant H2bpdcOMe linkers, demonstrating that these reactions can be used with known crystal engineering strategies. All transformations were fully compatible with the requirements to maintain MOF crystallinity and porosity as evidenced by surface area analysis and X-ray powder diffraction measurements. This work contributes to establishing the feasibility of high-temperature solid–gas manifolds for MOF PSM.

Although barium(II) ions play an important role in the natural weathering of the mineral uraninite (UO2+x) and are expected to therefore do the same for spent nuclear fuel in geological...