Single Crystal X-ray Diffraction Studies of Carbon Dioxide and Fuel-Related Gases Adsorbed on the Small Pore Scandium Terephthalate Metal Organic Framework, Sc2(O2CC6H4CO2)3
A novel metal-organic framework, MnCl2(BIPS)2•2CH3OH•2H2O (1) were synthesized from MnCl2 and a tetrahedral silicon-cored ligand, Me2Si(p-C6H4-imdazol-1-yl)2 (BIPS) under the slow diffusion method. The structure was determined by single-crystal X-ray diffraction. Complex 1 is a 2D sheet structure constructed from 1D chains with 34-atom metallamacrocycles.
The zirconium MOF NU-1000 was post-synthetically modified through solvothermal deposition to include the uranyl ion and characterized via single-crystal X-ray diffraction; photo-oxidation was also performed.
A metal–organic framework with a novel topology, poly[sesqui(μ2-4,4′-bipyridine)bis(dimethylformamide)bis(μ4-4,4′,4′′-nitrilotribenzoato)trizinc(II)], [Zn3(C21H12NO6)2(C10H8N2)1.5(C3H7NO)2]n, was obtained by the solvothermal method using 4,4′,4′′-nitrilotribenzoic acid and 4,4′-bipyridine (bipy). The structure, determined by single-crystal X-ray diffraction analysis, possesses three kinds of crystallographically independent ZnIIcations, as well as binuclear Zn2(COO)4(bipy)2paddle-wheel clusters, and can be reduced to a novel topology of a (3,3,6)-connected 3-nodal net, with the Schläfli symbol {5.62}4{52.6}4{58.87} according to the topological analysis.
The coordination polymer [Cu3(tci)2(phen)2] n (H3tci = 1,3,5-tris(2-carboxyethyl)isocyanurate; phen = 1,10-phenanthroline) has been synthesised. Single-crystal X-ray diffraction studies have shown that the polymer displays a 2-D metal–organic framework based on linear trinuclear copper cluster units, and its magnetic properties indicate antiferromagnetic interactions.
With the aid of a rotational C3-symmetric tricarboxytriphenylamine based ligand, a new Cd-MOF was synthesized and characterized by various spectroscopic techniques as well as by single-crystal X-ray diffraction analysis.
A very rare CO2-coordinated metal–organic framework was structurally confirmed by single-crystal X-ray diffraction. The CO2 ligand links two open Zn metal centers in an absolutely linear μ(O,O′) coordination mode with a CO distance of 1.107(4) Å. The new complex reported here is stable under ambient conditions and may provide a new strategy for CO2 fixation.
A novel 3D energetic metal–organic framework (MOF) of exceptionally high energy content, [Pb(BTO)(H2O)]n, was synthesized and structurally characterized by single crystal X-ray diffraction.
<div><p>Precisely locating extra-framework cations in anionic metal–organic framework compounds remains a long-standing, yet crucial, challenge for elucidating structure-performance relationships in functional materials. Single-crystal X-ray diffraction is one of the most powerful approaches for this task, but single crystals of frameworks often degrade when subjected to post-synthetic metalation or reduction. Here, we demonstrate the growth of sizable single crystals of the robust metal–organic framework Fe<sub>2</sub>(bdp)<sub>3</sub> (bdp<sup>2−</sup> = benzene-1,4-dipyrazolate) and employ single-crystal-to-single-crystal chemical reductions to access the solvated framework materials A<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub>∙<i>y</i>THF<sub> </sub>(A = Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>). X-ray diffraction analysis of the sodium and potassium congeners reveals that the cations are located near the center of the triangular framework channels and are stabilized by weak cation–π interactions with the framework ligands. Freeze-drying with benzene enables isolation of activated single crystals of Na<sub>0.5</sub>Fe<sub>2</sub>(bdp)<sub>3 </sub>and Li<sub>2</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> and the first structural characterization of activated metal–organic frameworks wherein extra-framework alkali metal cations are also structurally located. Comparison of the solvated and activated sodium-containing structures reveals that the cation positions differ in the two materials, likely due to cation migration that occurs upon solvent removal to maximize stabilizing cation–π interactions. Hydrogen adsorption data indicate that these cation-framework interactions are sufficient to diminish the effective cationic charge, leading to little or no enhancement in gas uptake relative to Fe<sub>2</sub>(bdp)<sub>3</sub>. In contrast, Mg<sub>0.85</sub>Fe<sub>2</sub>(bdp)<sub>3</sub> exhibits enhanced H<sub>2</sub> affinity and capacity over the non-reduced parent material. This observation shows that increasing the charge density of the pore-residing cation serves to compensate for charge dampening effects resulting from cation–framework interactions and thereby promotes stronger cation–H<sub>2</sub> interactions.</p></div>
Controlled Synthesis of Large Single Crystals of Metal‐Organic Framework CPO‐27‐Ni Prepared by a Modulation Approach: In situ Single Crystal X‐ray Diffraction Studies