Structural Disorder in High-Spin {Co^II₉W^V₆} (Core)-[Pyridine N-Oxides] (Shell) Architectures

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 {Co^II[Co^II₈(pyNO)₁₂(MeOH)₁₂][W^V(CN)₈]₆} (1) and {Co^II[Co^II₈(4-phpyNO)₇(MeOH)₁₇][W^V(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. View Full-Text