دورية أكاديمية
Discovery and In Situ Crystallization Studies of Cerium-Based Metal–Organic Frameworks with V‑Shaped Linker Molecules
| العنوان: | Discovery and In Situ Crystallization Studies of Cerium-Based Metal–Organic Frameworks with V‑Shaped Linker Molecules |
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| المؤلفون: | Jonas Gosch, Virginia Guiotto, Felix Steinke, Erik Svensson Grape, Cesare Atzori, Kalle Mertin, Tobias Otto, Niklas Ruser, Christoph Meier, Diletta Morelli Venturi, A. Ken Inge, Kirill A. Lomachenko, Valentina Crocellà, Norbert Stock |
| سنة النشر: | 2023 |
| مصطلحات موضوعية: | Biophysics, Biochemistry, Medicine, Physiology, Biotechnology, Inorganic Chemistry, Environmental Sciences not elsewhere classified, Chemical Sciences not elsewhere classified, Physical Sciences not elsewhere classified, shaped linker molecules, shaped linker molecule, different pore diameters, sorption measurements revealed, peculiar sorption behavior, framework structures consist, form framework structures, mofs occur exclusively, iv )- mofs, 4 ′-( hexafluoroisopropylidene, 4 ′- sulfonyldibenzoate, 2 , 1 , similar synthetic approach, ray photoelectron spectroscopy, iii oxidation state, 3d electron diffraction, 2 , situ crystallization studies, two porous ce, dependent mof crystallization |
| الوصف: | We report the discovery and characterization of two porous Ce(III)-based metal–organic frameworks (MOFs) with the V-shaped linker molecules 4,4′-sulfonyldibenzoate (SDB 2– ) and 4,4′-(hexafluoroisopropylidene)bis(benzoate) (hfipbb 2– ). The compounds of framework composition [Ce 2 (H 2 O)(SDB) 3 ] ( 1 ) and [Ce 2 (hfipbb) 3 ] ( 2 ) were obtained by using a synthetic approach in acetonitrile that we recently established. Structure determination of 1 was accomplished from 3D electron diffraction (3D ED) data, while 2 could be refined against powder X-ray diffraction (PXRD) data using the crystal structure of an isostructural La-MOF as the starting model. Their framework structures consist of chain-like inorganic building units (IBUs) or hybrid-BUs that are interconnected by the V-shaped linker molecules to form framework structures with channel-type pores. The composition of both compounds was confirmed by PXRD, elemental analysis, as well as NMR and IR spectroscopy. Interestingly, despite the use of (NH 4 ) 2 [Ce IV (NO 3 ) 6 ] in the synthesis, cerium ions in both MOFs occur exclusively in the + III oxidation state as determined by X-ray absorption near edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). Thermal analyses reveal remarkably high thermal stabilities of ≥400 °C for the MOFs. Initial N 2 sorption measurements revealed the peculiar sorption behavior of 2 which prompted a deeper investigation by Ar and CO 2 sorption experiments. The combination with nonlocal density functional theory (NL-DFT) calculations adds to the understanding of the nature of the different pore diameters in 2 . An extensive quasi-simultaneous in situ XANES/XRD investigation was carried out to unveil the formation of Ce-MOFs during the solvothermal syntheses in acetonitrile. The crystallization of the two Ce(III)-MOFs presented herein as well as two previously reported Ce(IV)-MOFs, all obtained by a similar synthetic approach, were studied. While the XRD patterns show time-dependent MOF crystallization, the XANES ... |
| نوع الوثيقة: | article in journal/newspaper |
| اللغة: | unknown |
| العلاقة: | https://figshare.com/articles/journal_contribution/Discovery_and_In_Situ_Crystallization_Studies_of_Cerium-Based_Metal_Organic_Frameworks_with_V_Shaped_Linker_Molecules/24727510Test |
| DOI: | 10.1021/acs.inorgchem.3c01862.s001 |
| الإتاحة: | https://doi.org/10.1021/acs.inorgchem.3c01862.s001Test https://figshare.com/articles/journal_contribution/Discovery_and_In_Situ_Crystallization_Studies_of_Cerium-Based_Metal_Organic_Frameworks_with_V_Shaped_Linker_Molecules/24727510Test |
| حقوق: | CC BY-NC 4.0 |
| رقم الانضمام: | edsbas.99482D3F |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acs.inorgchem.3c01862.s001 |
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