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J.G. acknowledges the financial support by the state of Schleswig-Holstein. We thank Tim Tjardts and the spectroscopic section of the Institute of Inorganic Chemistry of Kiel University for their support with various measurements. N.S. acknowledges financial support by the Deutsche Forschungsgemeinschaft (grant STO 643/15-1). V.C. and V.G. acknowledge support from the Project CH4.0 under the Italian MUR program '' Dipartimenti di Eccellenza 2023-2027 '' (CUP: D13C22003520001) and the Italian MUR through the Project PRIN 2020 doMino (ref 2020P9KBKZ). E.S.G. and A.K.I. acknowledge support from the Swedish Foundation for Strategic Research (SSF) for funding. European Synchrotron Radiation Facility (ESRF, Grenoble, France) is kindly acknowledged for providing beamtime for XAS/XRD measurements at BM23 beamline (CH-6121).

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Discovery and In Situ Crystallization Studies of Cerium-Based Metal-Organic Frameworks with V-Shaped Linker Molecules

Publicated to:Inorganic Chemistry. 62 (51): 20929-20939 - 2023-12-04 62(51), DOI: 10.1021/acs.inorgchem.3c01862

Authors: Gosch, Jonas; Guiotto, Virginia; Steinke, Felix; Svensson Grape, Erik; Atzori, Cesare; Mertin, Kalle; Otto, Tobias; Ruser, Niklas; Meier, Christoph; Morelli Venturi, Diletta; Inge, A Ken; Lomachenko, Kirill A; Crocella, Valentina; Stock, Norbert

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Abstract

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 (SDB2-) and 4,4 '-(hexafluoroisopropylidene)bis(benzoate) (hfipbb(2-)). The compounds of framework composition [Ce-2(H2O)(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 (NH4)(2)[Ce-IV(NO3)(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 degrees C for the MOFs. Initial N-2 sorption measurements revealed the peculiar sorption behavior of 2 which prompted a deeper investigation by Ar and CO2 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 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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