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Praseodymium Metallacrown-Based NMR Probe for Enantioselective Discrimination of Mandelate Anions in Water.
Inorg Chem
March 2023
G. A. Razuvaev Institute of Organometallic Chemistry RAS, Nizhny Novgorod 603950, Russia.
Recently, the enhanced interest in water-soluble aminohydroximate Ln(III)-Cu(II) metallacrowns (MC) is largely due to their fascinating structural chemistry, diverse properties and ease of synthesis. We examined the water-soluble praseodymium(III) alaninehydroximate complex Pr(HO)[15-MC-5]·3Cl () as a highly effective chiral lanthanide shift reagent for NMR analysis of the biologically relevant (R/S)-mandelate (MA) anions in aqueous media. The R-MA and S-MA enantiomers can be easily discriminated in the presence of small (1.
View Article and Find Full Text PDFLanthanide Identity Governs Guest-Induced Dimerization in Ln [15-MC -5]) Metallacrowns.
Chemistry
December 2021
Dipartimento di Scienze Chimiche, Università degli Studi di Catania, Viale Andrea Doria 6, 95125, Catania, Italy.
Series of lanthanide-containing metallic coordination complexes are frequently presented as structurally analogous, due to the similar chemical and coordinative properties of the lanthanides. In the case of chiral (Ln [15-MC -5]) metallacrowns (MCs), which are well established supramolecular hosts, the formation of dimers templated by a dicarboxylate guest (muconate) in solution of neutral pH is herein shown to have a unique dependence on the identity of the MC's central lanthanide. Calorimetric data and nuclear magnetic resonance diffusion studies demonstrate that MCs containing larger or smaller lanthanides as the central metal only form monomeric host-guest complexes whereas analogues with intermediate lanthanides (for example, Eu, Gd, Dy) participate in formation of dimeric host-guest-host compartments.
View Article and Find Full Text PDFCrystal structures of three anionic lanthanide-aluminium [3.3.1] metallacryptate complexes.
Acta Crystallogr E Crystallogr Commun
September 2020
Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA.
The three isomorphous [3.3.1] metallacryptate complexes bis-(pyridinium) di-aqua-dipyridine-hexa-kis-[μ-salicyl-hydroximato(3-)]bis-[μ-salicyl-hydroxim-ato(1-)]hexa-aluminiumgadolinium-pyridine-water (1/7.
View Article and Find Full Text PDFCrystal structures of two dysprosium-aluminium-sodium [3.3.1] metallacryptates that form two-dimensional sheets.
Acta Crystallogr E Crystallogr Commun
August 2020
Department of Chemistry and Biochemistry, Shippensburg University, Shippensburg, PA 17257, USA.
The two [3.3.1] metallacryptate complexes, namely, poly[[μ-acetato-hexa-kis-(μ-,-di-methyl-formamide)-bis-(,-di-methyl-formamide)bis-[salicyl-hydroxi-mato(2-)]hepta-kis-[salicyl-hydrox-im-ato(3-)]hexa-aluminium(III)dysprosium(III)penta-sodium(I)] ,-di-methyl-formamide tetra-solvate monohydrate], [DyAlNa(OAc)(Hshi)(shi)(DMF)]·4DMF·HO or {[DyAlNa(CHNO)(CHNO)(CHO)(CHNO)]·4CHNO·HO} , , and poly[[di-μ-acetato-nona-kis-(μ-,-di-methyl-form-amide)-octa-kis-(,-di-methyl-formamide)tetra-kis-[sali-cyl-hydroximato(2-)]tetra-deca-kis-[salicyl-hydroximato(3-)]dodeca-aluminium(III)didysprosium(III)deca-sodium(I)] ,-di-methyl-form-amide 6.
View Article and Find Full Text PDFExplaining How α-Hydroxamate Ligands Control the Formation of Cu(II)-, Ni(II)-, and Zn(II)-Containing Metallacrowns.
Inorg Chem
December 2019
Faculty of Chemistry , University of Wroclaw, 50-383 Wroclaw , Poland.
Four different crystal structures for quinolinehydroxamic acid () and picolinehydroxamic acid () MCs with Cu(II) and Ni(II), and solution studies on the formation of Cu(II), Ni(II), and Zn(II) MC complexes with , , and pyrazylohydroxamic acid () are described. In polynuclear complex , [Cu(-2H)(NO)(DMSO)](NO), the metallamacrocyclic cavity is formed by four Cu(II) ions and four doubly deprotonated hydroximate ligands, and the center of the cavity is occupied by the fifth Cu(II) ion coordinated by four hydroximate oxygen atoms. The complex , [Cu(-2H)(HO)(ClO)](ClO)·4HO, exhibits a dimeric structure based on two pentanuclear collapsed 12-MC-4 Cu(2H) fragments united by two chiral capping Cu(II) ions exo-coordinated to the peripheral vacant (O,O') chelating units of each tetranuclear collapsed MC moiety.
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