The combinations of Co(II), octacyanidotungstate(V), and monodentate pyridine N-oxide (pyNO) or 4-phenylpyridine N-oxide (4-phpyNO) led to crystallization of novel crystalline phases {CoII[CoII8(pyNO)12(MeOH)12][WV(CN)8]6} (1) and {CoII[CoII8(4-phpyNO)7(MeOH)17][WV(CN)8]6}·7MeOH·(4-phpyNO)3 (2). In both architectures, metal-cyanide clusters are coordinated by N-oxide ligands in a simple monodentate manner to give the spherical objects of over 1 nm core diameter and about 2.2 nm (1) and 3 nm (2) 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 1, the π-π interactions between the pyNO ligands attached to the same metal centers are suggested for the first time. In 2, 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 M9M'6-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.
Keywords: crystal engineering; magnetic coordination materials; molecular disorder; octacyanidometalates; polynuclear clusters; surface decoration.