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Taking the Third Route for Construction of POMOFs: The First Use of Carboxylate-Functionalized Mn$^{III}$Anderson-Evans POM-Hybrid Linkers and Lanthanide Nodes

Merkel, Marcel P. 1,2; Anson, Christopher E. 1; Kostakis, George E.; Powell, Annie K. 1,2
1 Institut für Anorganische Chemie (AOC), Karlsruher Institut für Technologie (KIT)
2 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)


The purpose of the present contribution is to illustrate how to design and grow crystals of POMOFs based on POM-hybrid linkers with lanthanide ions as nodes. Thus, the Mn$^{III}$-centered Anderson–Evans polyoxometalate (Mn-A-E-POM) was functionalized with 4-(((1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)amino)methyl)benzoic acid (H$_{4}^{-}$L) to afford the hybrid inorganic–organic POM [N(n-C$_{4}$H$_{9}$)$_{4}$]$_{4}$[(MnMo$_{6}$O$_{18}$)(HL)(L)] (1), which in turn reacts with lanthanide salts and yields two three-dimensional frameworks with the general formulas Ln(DMF)$_{6}$Ln(DMF)$_{5}$Ln$_{3}$(DMF)$_{10}$[(MnMo$_{6}$O$_{18}$)(L)$_{2}$]$_{3}$·xDMF (2; Ln = La–Nd) and [Ln(DMF)4(H2O)]2[Ln3(DMF)6][(MnMo6O18)(L)2]3·xDMF (3; Ln = Y, Sm–Lu). The differentiation in these two families results from the lanthanide contraction. The crystallization process is crucial for obtaining these two families in a bulk pure phase. Family 2 can be obtained by stirring, while for family 3 the less energy demanding layering method proved to be the most efficient pathway. Notably, the change in the ionic radii causes a change in space group (from P2$_{1}$ (family 2) to P2$_{1}$/c (family 3); however, the topology of the frameworks is unaffected.

Postprint §
DOI: 10.5445/IR/1000133858
Veröffentlicht am 01.01.2023
DOI: 10.1021/acs.cgd.0c01138
Zitationen: 6
Web of Science
Zitationen: 5
Zitationen: 9
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2021
Sprache Englisch
Identifikator ISSN: 1528-7483, 1528-7505
KITopen-ID: 1000133858
HGF-Programm 43.32.01 (POF IV, LK 01) Molecular Materials Basis for Optics & Photonics
Erschienen in Crystal Growth and Design
Verlag American Chemical Society (ACS)
Band 21
Heft 6
Seiten 3179–3190
Nachgewiesen in Dimensions
Web of Science
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