Host–Guest‐Induced Environment Tuning of 3d Ions in a Polyoxopalladate Matrix

A series of unprecedented supramolecular associates of phenylarsonate‐capped {MIIPdII12O8}‐type (M=Co, Ni and Zn) polyoxopalladates with α‐cyclodextrins (α‐CD) was obtained and characterized in the solid state (single‐crystal X‐ray diffraction (XRD), FT‐IR spectroscopy, elemental and thermogravimetr...

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Veröffentlicht in:Chemistry : a European journal Jg. 24; H. 67; S. 17767 - 17778
Hauptverfasser: Stuckart, Maria, Izarova, Natalya V., van Leusen, Jan, Smekhova, Alevtina, Schmitz‐Antoniak, Carolin, Bamberger, Heiko, van Slageren, Joris, Santiago‐Schübel, Beatrix, Kögerler, Paul
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Germany Wiley Subscription Services, Inc 03.12.2018
Schlagworte:
Aqueous solutions
Cadmium
Chemistry
Cyclodextrin
Cyclodextrins
Dichroism
Electronic structure
Infrared spectroscopy
Linear dichroism
Magnetic measurement
Magnetic properties
Metal ions
NMR
Nuclear magnetic resonance
Organic chemistry
polyoxometalates
Spectrum analysis
Superconducting quantum interference devices
supramolecular assembly
Transition metals
Vapor phases
X ray spectra
X-ray diffraction
supramolecular assembly
magnetic properties
polyoxometalates
cyclodextrin
transition metals
ISSN:0947-6539, 1521-3765, 1521-3765
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Zusammenfassung:A series of unprecedented supramolecular associates of phenylarsonate‐capped {MIIPdII12O8}‐type (M=Co, Ni and Zn) polyoxopalladates with α‐cyclodextrins (α‐CD) was obtained and characterized in the solid state (single‐crystal X‐ray diffraction (XRD), FT‐IR spectroscopy, elemental and thermogravimetric (TGA) analyses), in aqueous solution (1H and 13C NMR) and in the gas phase (ESI‐MS). The non‐covalent host–guest interactions between the organopolyoxoanions and α‐CD rings alter the O8 coordination environment of a 3d transition metal ion (MII) situated at the center of a cuboid polyoxododecapalladate shell. This synthetically controlled “chemical pressure” effectively induces axial distortion of the otherwise cubic polyoxopalladate environment between two trans‐positioned α‐CD moieties. Its effect on the magnetic properties and the electronic structure of the CoII derivative was assessed in a combined SQUID magnetometry, EPR, X‐ray magnetic circular/linear dichroism (XMCD/XMLD), and X‐ray absorption near‐edge structure (XANES) spectroscopy study. The sweet pressure is on (the noble cube): Modification of the coordination environment of the transition metal ion incorporated in the center of a polyoxometalate cage can be achieved via non‐covalent interactions, as demonstrated by a novel family of supramolecular {MPd12(AsPh)8}⊂2(α‐CD) host–guest associates of transition‐metal‐centered, phenylarsonate‐capped polyoxopalladates with α‐cyclodextrins.
Bibliographie:Gewidmet unserem Freund und Kupferstecher Wolfgang Bensch zum 65. Geburtstag.
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ISSN:0947-6539
1521-3765
1521-3765
DOI:10.1002/chem.201803531