Tri‐ and Pentanuclear Complexes Derived from Manganese(III) Schiff Base and Hexacyanoferrate(III) Building Blocks

Abstract

A tri‐ and a pentanuclear cyanido‐bridged complex based on manganese(III) Schiff base and hexacyanoferrate(III) units, namely, [{Mn(naphtmen)}2{Fe(CN)6}][Mn(naphtmen)(CH3OH)2]2ClO4·5CH3OH·H2O [1; naphtmen2– = N,N′‐(1,1,2,2‐tetramethylethylene)bis(naphthylideneiminato) dianion] and [{Mn(naphtmen)}4{Fe(CN)6}]ClO4 (2), were synthesized and structurally characterized by X‐ray single‐crystal diffraction. The structural analyses show that 1 consists of linear trinuclear clusters of [{Mn(naphtmen)}2{Fe(CN)6}]– anions, which are further linked into one‐dimensional chains by the out‐of‐plane biphenolate bridges. In 2, magnetically isolated cyanido‐bridged pentanuclear {[Mn(naphtmen)]4[Fe(CN)6]}+ cations were obtained. The temperature‐dependent magnetic susceptibilities indicate that the exchange interactions between the FeIII and MnIII ions through the cyanido bridges are ferromagnetic in 1 and 2. The magnetic fittings for 1 and 2 gave magnetic coupling constants JMnFe = 6.68 and 4.31 cm–1, respectively. Complex 2 exhibits a clear frequency‐dependent alternating‐current (AC) magnetic susceptibility below 3.5 K, which is due to single‐molecule magnet behavior with Ueff = 23.4 cm–1 and τ0 = 7.5 × 10–10 s.