New family of bi-, tetra-, penta-, and hexanickel cage-like phenylsilsesquioxanes 1-3 (Fig.1) was obtained by self-assembling and transmetalation procedures. Their crystal structures were established by single crystal X-ray analysis; and features of crystal packing relevant to the networks formation were studied by a topological analysis. The geometry of metallosiloxane units 1 and 2 could be assigned to a distorted prism, with prominent shift of prism’ bases (silsesquioxane ligands) from the vertical axis. In turn, molecular architecture of compound 3 is regular prismatic one. Compounds 1-3 form extended networks in crystal via coordination bonds between alkali metals (Na, K, Cs) and oxygen atoms of siloxanolate moieties or coordinated solvent molecules (see, for instance Fig. 2). The investigation of magnetic properties revealed the presence of ferro- or antiferromagnetic interactions between Ni(II) ions giving rise in the most cases the presence of a slow relaxation of the magnetization, which can arise from the spin frustration.
The work was supported by the Russian Foundation for Basic Research (projects 16-29-05180 and 16-03-00206).