ИСТИНА

In the present work we have investigated the cation-induced assembling of crown-substituted REE(III) trisphthalocyaninates as an approach which can be perspective to trigger SMM properties of these complexes.1 The interaction of potassium salts with two types of heteroleptic 15-crown-5- substituted yttrium trisphthalocyaninates as diamagnetic references, namely [(15C5)4Pc]Y(Pc)Y(Pc) (1) and [(15C5)4Pc]Y[(15C5)4Pc]Y(Pc)2 (2) was investigated both by 1H- and DOSY NMR in solution and by single-crystal X-ray diffraction analysis in solid state. It was found that the complex (1) forms supramolecular dimer (1)2⋅4K+ consisting of six phthalocyanine decks. Its structural characteristics suggest the possibility of the magnetic-dipolar f-f interaction between the ions at M1 and M2 cites, as well as additional weaker coupling between ions at M2 and M2′ cites, which can be observed in the case of isostructural Tb or Dy complexes. In the case of the complex (2) there was observed the intercalation of K+ into the space between the neighbouring crown-ether rings. Instead of the formation of supramolecular dimers, there was obtained the monomeric supramolecular assembly (2)⋅4K+ with the square-prismatic polyhedron of the Y(III) ion sandwiched between two crown-substituted ligands and square-antiprismatic polyhedron of Y(III) ion in asymmetric surrounding. It is expected that such supramolecular switching of the Ln(III) coordination polyhedron can be used to tune the relaxation rate of SMMs based on triple-decker crown-phthalocyaninates formed by Tb(III) and Dy(III). The hydrodynamic radii of assemblies (1)2⋅4K+ and (2)⋅4K+ deduced from DOSY are in good agreement with the X-ray structure, suggesting that these assemblies are formed both in solution and in solid state.