Structural Disorder in High-Spin {Co II 9 W V 6 } ( Core )-[Pyridine N-Oxides] ( Shell ) Architectures

The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine -oxide (pyNO) or 4-phenylpyridine -oxide (4-phpyNO) led to crystallization of novel crystalline phases {Co [Co (pyNO) (MeOH) ][W (CN) ] } ( ) and {Co [Co (4-phpyNO) (MeOH) ][W (CN) ] }·7MeOH·(4-phpyNO) ( ). In both archite...

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Veröffentlicht in:Molecules (Basel, Switzerland) Switzerland), 2020-01, Vol.25 (2), p.251
Hauptverfasser: Liberka, Michal, Kobylarczyk, Jedrzej, Podgajny, Robert
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Sprache:eng
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Zusammenfassung:The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine -oxide (pyNO) or 4-phenylpyridine -oxide (4-phpyNO) led to crystallization of novel crystalline phases {Co [Co (pyNO) (MeOH) ][W (CN) ] } ( ) and {Co [Co (4-phpyNO) (MeOH) ][W (CN) ] }·7MeOH·(4-phpyNO) ( ). In both architectures, metal-cyanide clusters are coordinated by -oxide ligands in a simple monodentate manner to give the spherical objects of over 1 nm core diameter and about 2.2 nm ( ) and 3 nm ( ) of the total diameter, terminated with the aromatic rings. The supramolecular architecture is dominated by dense and rich π-π interaction systems. Both structures are characterized by a significant structural disorder in ligand shell, described with the suitable probability models. For , the π-π interactions between the pyNO ligands attached to the same metal centers are suggested for the first time. In , 4-phpyNO acts as monodentate ligand and as the crystallization molecule. Magnetic studies indicate the high-spin ground state due to the ferromagnetic interactions Co(II)-W(V) through the cyanido bridges. Due to the high symmetry of the clusters, no signature of slow magnetic relaxation was observed. The characterization is completed by solid-state IR and UV-Vis-NIR spectroscopy. The conditions for the stable M M' -based crystals formation are synthetically discussed in terms of the type of capping ligands: monodentate, bridging, and chelating. The potential of the related polynuclear forms toward the magnetism-based functional properties is critically indicated.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules25020251