Inorg Chem
Institut für Anorganische Chemie, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Str. 2, 24118 Kiel, Germany.
Published: December 2023
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) and 4,4'-(hexafluoroisopropylidene)bis(benzoate) (hfipbb). The compounds of framework composition [Ce(HO)(SDB)] () and [Ce(hfipbb)] () were obtained by using a synthetic approach in acetonitrile that we recently established. Structure determination of was accomplished from 3D electron diffraction (3D ED) data, while 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)[Ce(NO)] 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 sorption measurements revealed the peculiar sorption behavior of which prompted a deeper investigation by Ar and CO 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 . 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 data reveal the presence of Ce(III) intermediates and their subsequent conversion to the MOFs. The addition of acetic acid in combination with the V-shaped linker molecule was identified as the crucial factor for the formation of the crystalline Ce(III/IV)-MOFs.
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http://dx.doi.org/10.1021/acs.inorgchem.3c01862 | DOI Listing |
Acc Chem Res
November 2024
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Mikrochim Acta
September 2024
Nano-Catalysis Research Lab, Department of Chemistry, School of Advanced Sciences, Vellore Institute of Technology, Vellore, 632014, Tamilnadu, India.
A novel electrochemical sensor is constructed by modifying the glassy carbon electrode (GCE) using a binder-free metal-organic framework of V-shaped linker 4,4'oxybis(benzoic acid) (OBA) and various transition metals (M-Zn, Mn, or Ni). The hydrothermally synthesized M-OBA MOFs demonstrated superior electron transfer ability and enhanced electro-reduction behaviour, making it highly effective for metronidazole (MTZ) detection. The optimized sensor demonstrated a linear response from 0.
View Article and Find Full Text PDFJ Am Chem Soc
September 2024
School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Frontiers Science Center for Transformative Molecules, State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, China.
Covalent organic frameworks (COFs) have potential applications in a wide range of fields. However, it remains a critical challenge to constrain their covalent expansions in the one-dimensional (1D) direction. Here, we developed a general approach to fabricate 15 different highly crystalline COFs with zigzag-packed 1D porous organic chains through the condensation of V-shaped ditopic linkers and X-shaped tetratopic knots.
View Article and Find Full Text PDFJ Biol Chem
June 2024
Department of Molecular and Cellular Oncology, The University of Texas MD Anderson Cancer Center, Houston, Texas, USA; Molecular Biophysics and Integrated Bioimaging, Lawrence Berkeley National Laboratory, Berkeley, California, USA; Department of Cancer Biology, University of Texas MD Anderson Cancer Center, Houston, Texas, USA. Electronic address:
Activating signal co-integrator complex 1 (ASCC1) acts with ASCC-ALKBH3 complex in alkylation damage responses. ASCC1 uniquely combines two evolutionarily ancient domains: nucleotide-binding K-Homology (KH) (associated with regulating splicing, transcriptional, and translation) and two-histidine phosphodiesterase (PDE; associated with hydrolysis of cyclic nucleotide phosphate bonds). Germline mutations link loss of ASCC1 function to spinal muscular atrophy with congenital bone fractures 2 (SMABF2).
View Article and Find Full Text PDFACS Appl Mater Interfaces
April 2024
Department of Chemistry, Research Institute for Natural Sciences, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea.
In this study, two novel multiple resonance (MR) emitters, DtCzBN and Cy-DtCzBN, were designed based on the well-known BCzBN structure and synthesized for narrowband solution-processed organic light-emitting diodes (OLEDs). Cy-DtCzBN possesses a dimeric V-shaped structure formed by coupling two individual DtCzBN units via a nonconjugated cyclohexane linker. When compared with DtCzBN, Cy-DtCzBN, as a medium-sized molecule, was found to maintain the optical and photophysical properties of the corresponding monomeric unit, DtCzBN, but exhibits high thermal stability, excellent solubility, and good film-forming ability.
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