An Influence of Fluorinated Alkyl Substituents on Structure and Magnetic Properties of Mn(II) Complexes with Pyrazolyl-Substituted Nitronyl Nitroxides.

New complexes of manganese(II) hexafluoroacetylacetonate [Mn(hfac)₂] with 2-(1-R-3-pyrazol-4-yl)-4,4,5,5-tetramethyl-2-imidazoline-3-oxide-1-oxyl (R = CHF₂, CH₂CH₂F, CH₂CHF₂ or CH₂CF₃) were synthesised and characterised structurally and magnetically. All complexes were prepared under similar conditions. Nonetheless, their crystal structures were considerably different. Depending on the structure of fluorinated alkyl substituent R, the complexation reaction led to complexes of three types: chain-polymeric complexes with the head-to-head or head-to-tail motif and complexes of molecular structure. All complexes show strong antiferromagnetic behaviour in a high-temperature region (150–300 K) and weak ferro- or antiferromagnetic exchange interactions at low temperatures. The stronger antiferromagnetic exchange, −101.7 ± 1.5 or −136 ± 10 cm⁻¹, −82.3 ± 1.3 cm⁻¹ and −87.4 ± 1.3 cm⁻¹, was attributed to the magnetic interaction in three- or two-spin clusters: {>N∸O–Mn²⁺–O∸N<} or {>N∸O–Mn²⁺}, respectively. The weaker antiferromagnetic interaction, −0.005, between three-spin clusters or ferromagnetic interactions, 0.18–0.81 cm⁻¹, between two-spin clusters are realised through the pyrazole ring or intermolecular contacts. [ABSTRACT FROM AUTHOR]