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Host–Guest‐Induced Environment Tuning of 3d Ions in a Polyoxopalladate Matrix
Author(s) -
Stuckart Maria,
Izarova Natalya V.,
van Leusen Jan,
Smekhova Alevtina,
SchmitzAntoniak Carolin,
Bamberger Heiko,
van Slageren Joris,
SantiagoSchübel Beatrix,
Kögerler Paul
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803531
Subject(s) - thermogravimetric analysis , crystallography , supramolecular chemistry , xanes , electron paramagnetic resonance , spectroscopy , aqueous solution , chemistry , magnetic circular dichroism , materials science , crystal structure , nuclear magnetic resonance , spectral line , physics , organic chemistry , quantum mechanics , astronomy
A series of unprecedented supramolecular associates of phenylarsonate‐capped {M II Pd II 12 O 8 }‐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 ( 1 H and 13 C NMR) and in the gas phase (ESI‐MS). The non‐covalent host–guest interactions between the organopolyoxoanions and α‐CD rings alter the O 8 coordination environment of a 3d transition metal ion (M II ) 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 Co II 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.