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Supramolecular Recognition Influences Magnetism in [X@HV IV 8 V V 14 O 54 ] 6− Self‐Assemblies with Symmetry‐Breaking Guest Anions
Author(s) -
Yu. Monakhov Kirill,
Linnenberg Oliver,
Kozłowski Piotr,
van Leusen Jan,
Besson Claire,
Secker Tim,
Ellern Arkady,
López Xavier,
Poblet Josep M.,
Kögerler Paul
Publication year - 2015
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.201403858
Subject(s) - supramolecular chemistry , isostructural , diamagnetism , magnetism , crystallography , valence (chemistry) , delocalized electron , van der waals force , chemistry , ion , unpaired electron , magnetic susceptibility , valence electron , stereochemistry , electron , electron paramagnetic resonance , physics , crystal structure , nuclear magnetic resonance , magnetic field , condensed matter physics , molecule , organic chemistry , quantum mechanics
Abstract Mixed‐valence polyoxovanadates(IV/V) have emerged as one of the most intricate class of supramolecular all‐inorganic host species, able to encapsulate a wide variety of smaller guest templates during their self‐assembly formation process. As showcased herein, the incorporation of guests, though governed solely by ultra‐weak electrostatic and van der Waals interactions, can cause drastic effects on the electronic and magnetic characteristics of the shell complex of the polyoxovanadate. We address the question of methodology for the magnetochemical analysis of virtually isostructural {V IV/V 22 O 54 }‐type polyoxoanions of D 2 d symmetry enclosing diamagnetic VO 2 F 2 − ( C 2 v ), SCN − ( C ∞v ), or ClO 4 − ( T d ) template anions. These induce different polarization effects related to differences in their geometric structures, symmetry, ion radii, and valence shells, eventually resulting in a supramolecular modulation of magnetic exchange between the V(3d) electrons that are partly delocalized over the {V 22 O 54 } shells. We also include the synthesis and characterization of the novel [V V O 2 F 2 @HV IV 8 V V 14 O 54 ] 6− system that comprises the rarely encountered discrete difluorovanadate anion as a quasi‐isolated guest species.