Synthesis, Structure, and Magnetic Properties of Three 1D Chain Complexes Based on High-Spin Metal–Cyanide Clusters: [MnIII 6MIII] (M = Cr, Fe, Co)

• Published in: Inorganic chemistry 2011-08, Vol.50 (15), p.6868-6877
• Main Authors: Zhou, Hong-Bo, Wang, Jun, Wang, Hui-Sheng, Xu, Yong-Lu, Song, Xiao-Jiao, Song, You, You, Xiao-Zeng
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic102527h

On the basis of high-spin metal–cyanide clusters of MnIII 6MIII (M = Cr, Fe, Co), three one-dimensional (1D) chain complexes, [Mn(salen)]6[Cr(CN)6]2·6CH3OH·H2O (1), [Mn(5-CH3)salen)]6[Fe(CN)6]2·2CH3CN·10H2O (2), and [Mn(5-CH3)salen)]6[Co(CN)6]2·2CH3CN·10H2O (3) [salen = N,N′-ethylenebis(salicylideneiminato) dianion], have been synthesized and characterized structurally as well as magnetically. Complexes 2 and 3 are isomorphic but slightly different from complex 1. All three complexes contain a 1D chain structure which is comprised of alternating high-spin metal–cyanide clusters of [Mn6M]3+ and a bridging group [M(CN)6]3– in the trans mode. Furthermore, the three complexes all exhibit extended 3D supramolecular networks originating from short intermolecular contacts. Magnetic investigation indicates that the coupling mechanisms are intrachain antiferromagnetic interactions for 1 and ferromagnetic interactions for 2, respectively. Complex 3 is a magnetic dilute system due to the diamagnetic nature of CoIII. Further magnetic investigations show that complexes 1 and 2 are dominated by the 3D antiferromagnetic ordering with T N = 7.2 K for 1 and 9.5 K for 2. It is worth noting that the weak frequency-dependent phenomenon of AC susceptibilities was observed in the low-temperature region in both 1 and 2, suggesting the presence of slow magnetic relaxations.