Tacticity versus dimension of the extended structures in the crystals of heterospin magnets made of transition-metal complexes with the poly(aminoxyl) radical

Abstract

Bis- and tris(aminoxyl) radicals and di(4-pyridyl)diazomethane form crystalline complexes with extended structures upon reaction with [M(hfac)₂] (M=Mn^II or Cu^II, and hfac=hexafluoroacetylacetonate). Organic 2p and metal 3d spins in these complexes order at 3.4–46 K depending on the dimensions of the extended structures and the magnitude of exchange coupling between the adjacent spins. In the crystals of one-dimensional systems, the polymeric chains are isotactic in that free radical or precursor ligands and/or metal centres have the same chirality along any given chain. The polymeric chains are syndiotactic and cross link to form two-dimensional honeycomb or three-dimensional crossed parallel networks.