Peculiarities of synthesis of chain polymeric, copper(II) hexafluoroacetylacetonate based complexes with stable nitroxyl radicals and the results of studies on correlations between the magnetic properties and structure of these compounds are summarized. Temperature variation causes structural rearrangements in the solid phases of the compounds, accompanied by the magnetic effects similar to spin crossover phenomena. Magnetic anomalies induced by phase transitions originate from specific motions in the Jahn-Teller coordination units containing two types of exchange clusters, Cu 2+ -O • -N< or >N-• O-Cu 2+ -O • -N<, and are ac companied by significant changes in the crystal volume after multiple cooling/heating cycles. Chemical methods of controlling the character and temperature of spin transitions by both the formation of solid solutions of mixed metal hexafluoroacetylacetonates with the same nitroxyl radical, {Cu 1-x M x (hfac) 2 L} (M = Mn, Ni, Co), and by the formation of solid solutions based on copper(II) hexafluoroacetylacetonate with different nitroxyl radicals, {Cu(hfac) 2 L x L´1 -x }, are discussed. Specific influence of isotope substitution CH 3 → CD 3 in the paramagnetic ligand on both the structure of the heterospin polymer chain and the temperature of the magnetic anomaly is discussed.

The stereochemically flexible Cu(hfac)(2) metal-ligand system when combined with polyfunctional nitroxides leads to a variety of solids with varying structure and composition. While investigating the products of Cu(hfac)(2) interaction with spin-labeled pyrazole 4,4,5,5-tetramethyl-2-(1-methyl-1H-pyrazol-4-yl)-imidazoline-3-oxide-1-oxyl, we have isolated a family of (12) heterospin compounds differing in structure and composition in the solid state. In synthetic systems, these compounds often cocrystallize and must be separated mechanically. It is also shown that minor variation of the structure of the solid heterospin complex can substantially change the magnetic properties of compounds.

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