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

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• 作者：Meng-Jiao Zhang ; Yu-Ye Zhang ; Chun Yang ; Qing-Lun Wang and Dai-Zheng Liao
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：2016
• 期：22
• 页码：3620-3628
• 全文大小：2320K
• ISSN：1099-0682c

文摘

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; naphtmen^2– = 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 Fe^III and Mn^III ions through the cyanido bridges are ferromagnetic in 1 and 2. The magnetic fittings for 1 and 2 gave magnetic coupling constants J_MnFe = 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 U_eff = 23.4 cm^–1 and τ₀ = 7.5 × 10^–10 s.