Metal-Organic Frameworks with Hexakis(4-carboxyphenyl)benzene : Extensions to Reticular Chemistry and Introducing Foldable Nets
| Autor: | Lars Öhrström, Jerker Mårtensson, Per Malmberg, Christine J. McKenzie, Erik Svensson Grape, Ocean Cheung, Steffen Brülls, A. Ken Inge, Francoise M. Amombo Noa |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Solid-state chemistry
Chemistry Formic acid Materialkemi Sorption General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Article Catalysis Dimethylacetamide 0104 chemical sciences chemistry.chemical_compound Crystallography Colloid and Surface Chemistry Materials Chemistry Dimethylformamide Metal-organic framework Isostructural Benzene |
| Zdroj: | Amombo Noa, F M, Grape, E S, Brülls, S M, Cheung, O, Malmberg, P, Inge, A K, McKenzie, C, Mårtensson, J & Öhrström, L 2020, ' Metal–Organic Frameworks with Hexakis(4-carboxyphenyl)benzene: Extensions to Reticular Chemistry and Introducing Foldable Nets ', Journal of the American Chemical Society, vol. 142, no. 20, pp. 9471-9481 . https://doi.org/10.1021/jacs.0c02984 Journal of the American Chemical Society |
| Popis: | Nine metal-organic frameworks have been prepared with the hexagon-shaped linker 1,2,3,4,5,6-hexakis(4-carboxyphenyl)-benzene (H(6)cpb) by solvothermal reactions in dimethylformamide (dmf) or dimethylacetamide (dmac) with acetic acid or formic acid as modulators: [Bi-2(cpb)(acetato)(2)(dmf)(2)]center dot 2dmf CTH-6 forms a rtl-net; 2(H2NMe2)[Cu-2(cpb)] CTH-7 forms a kgd-net; [Fe-4(cpb)-(acetato)(2)(dmf)(4)] CTH-8 and [Co-4(cpb)(acetato)(2)(dmf)(4)] CTH-9 are isostructural and form yav-nets; 2(HNEt3)[Fe-2(cpb)] CTH-10 and the two polymorphs of 2(H2NMe2)[Zn-2(cpb)]center dot 1.5dmac, Zn-MOF-888 and CTH-11, show kgd-nets; [Cu-2(cpb)-(acetato)(2)(dmf)(2)]center dot 2dmf, CTH-12, forms a mixed coordination and hydrogen-bonded sql-net; and 2(H2NMe2)[Zn-2(cpb)] CTH-13, a similarly mixed yav-net. Surface area values (Brunauer-Emmett-Teller, BET) range from 34 m(2) g(-1) for CTH-12 to 303 m(2) g(-1) for CTH-9 for samples activated at 120 degrees C in dynamic vacuum. All compounds show normal (10-fold higher) molar CO2 versus N-2 uptake at 298 K, except the 19-fold CO2 uptake for CTH-12 containing Cu(II) dinuclear paddle-wheels. We also show how perfect hexagons and triangles can combine to a new 3D topology laf, a model of which gave us the idea of foldable network topologies, as the laf-net can fold into a 2D form while retaining the local geometry around each vertex. Other foldable nets identified are cds, cds-a, ths, sqc163, clh, jem, and tfc covering the basic polygons and their combinations. The impact of this concept on "breathing" MOFs is discussed. I-2 sorption, both from gas phase and from MeOH solution, into CTH-7 were studied by time of flight secondary ion mass spectrometry (ToF-SIMS) on dried crystals. I-2 was shown to have penetrated the crystals, as layers were consecutively peeled off by the ion beam. We suggest ToF-SIMS to be a method for studying sorption depth profiles of MOFs. |
| Databáze: | OpenAIRE |
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