23 research outputs found

    A Thorium Metal-Organic Framework with Outstanding Thermal and Chemical Stability.

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    A new thorium metal-organic framework (MOF), Th(OBA)2 , where OBA is 4,4'-oxybis(benzoic) acid, has been synthesized hydrothermally in the presence of a range of nitrogen-donor coordination modulators. This Th-MOF, described herein as GWMOF-13, has been characterized by single-crystal and powder X-ray diffraction, as well as through a range of techniques including gas sorption, thermogravimetric analysis (TGA), solid-state UV/Vis and luminescence spectroscopy. Single-crystal X-ray diffraction analysis of GWMOF-13 reveals an interesting, high symmetry (cubic Ia 3 ‾ d) structure, which yields a novel srs-a topology. Most notably, TGA analysis of GWMOF-13 reveals framework stability to 525 °C, matching the thermal stability benchmarks of the UiO-66 series MOFs and zeolitic imidazolate frameworks (ZIFs), and setting a new standard for thermal stability in f-block based MOFs

    Probing Hydrogen and Halogen-Oxo Interactions in Uranyl Coordination Polymers:A Combined Crystallographic and Computational Study

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    The syntheses and crystal structures of four compounds containing the UO22+ cation and either benzoic acid (1), m-chlorobenzoic acid (2), m-bromobenzoic acid (3), or m-iodobenzoic acid (4) are described and the vibrational spectroscopic properties for compounds 3 and 4 are reported. Single crystal X-ray diffraction analysis of these materials shows that uranyl oxo atoms are engaged in non-covalent assembly via either hydrogen (1 and 2) or halogen bonding (3 and 4) interactions. The halogen bonding in compounds 3 and 4 is notable as the crystallographic metric percentage of the sum of the van der Waals radii indicates these interactions are of similar strength. Characteristics of the halogen-oxo interactions of 3 and 4 were probed via Raman and infrared spectroscopy, which revealed significant differences in stretching frequency values for the two compounds. Additionally, compounds 3 and 4 were characterized via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis, which indicated that the I-oxo interaction in 4 is likely the stronger of the two interactions, with differences between the two interactions resulting from both inductive effects and halogen polarizability

    How to Bend the Uranyl Cation via Crystal Engineering

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    Bending the linear uranyl (UO22+) cation represents both a significant challenge and opportunity within the field of actinide hybrid materials. As part of related efforts to engage the nominally terminal oxo atoms of uranyl cation in noncovalent interactions, we synthesized a new uranyl complex, [UO2(C12H8N2)2(C7H2Cl3O2)2]·2H2O (complex 2), that featured both deviations from equatorial planarity and uranyl linearity from simple hydrothermal conditions. Based on this complex, we developed an approach to probe the nature and origin of uranyl bending within a family of hybrid materials, which was done via the synthesis of complexes 1–3 that display significant deviations from equatorial planarity and uranyl linearity (O–U–O bond angles between 162° and 164°) featuring 2,4,6-trihalobenzoic acid ligands (where Hal = F, Cl, and Br) and 1,10-phenanthroline, along with nine additional “nonbent” hybrid materials that either coformed with the “bent” complexes (4–6) or were prepared as part of complementary efforts to understand the mechanism(s) of uranyl bending (7–12). Complexes were characterized via single crystal X-ray diffraction and Raman, infrared (IR), and luminescence spectroscopy, as well as via quantum chemical calculations and density-based quantum theory of atoms in molecules (QTAIM) analysis. Looking comprehensively, these results are compared with the small library of bent uranyl complexes in the literature, and herein we computationally demonstrate the origin of uranyl bending and delineate the energetics behind this process

    Exploring the promotion of synthons of choice: halogen bonding in molecular lanthanide complexes characterized via X-ray diffraction, luminescence spectroscopy, and magnetic measurements

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    Promotion of a synthon of choice for the non-covalent assembly of lanthanide tectons represents both a noteworthy challenge and opportunity within LnIII hybrid materials. We have developed a system, wherein some control can be exercised over supramolecular assembly and, as part of continued efforts to improve this process we have generated a family of ten new lanthanide (Ln = Sm3+ – Lu3+) 2,4,6-trichlorobenzoic acid-1,10-phenanthroline molecular complexes. Delineation of criteria for promoting assembly via halogen based interactions was introduced previously and is refined herein based on the characterization of complexes 1–10 via single-crystal X-ray diffraction. Direct comparison of means of supramolecular assembly for 1–10 with isostructural Ln-p-chlorobenzoic acid-1,10-phenanthroline analogues verifies that increasing the number of halogen atoms at the periphery of a tecton is one route that increases the frequency of halogen bonding interactions. Additionally, solid-state visible and near-IR photoluminescence and luminescent lifetime data were collected for complexes 1 (Sm3+), 2 (Eu3+), 4 (Tb3+), 5 (Dy3+), 6 (Ho3+), 7 (Er3+), and 9 (Yb3+) and characteristic emission was observed for all complexes except 6. Further, direct current magnetic susceptibility measurements were carried out for complexes 5 (Dy3+) and 7 (Er3+), and two slow magnetic relaxation processes were characterized using alternating current magnetic susceptibility measurements for 5
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