Structural Conversion and Magnetic Studies of Low-Dimensional LnIII/MoV/IV(CN)8 (Ln = Gd–Lu) Systems: From Helical Chain to Trinuclear Cluster

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• 作者：Hu Zhou ; Qi Chen ; Hong-Bo Zhou ; Xiao-Zhen Yang ; You Song ; Ai-Hua Yuan
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：March 2, 2016
• 年：2016
• 卷：16
• 期：3
• 页码：1708-1716
• 全文大小：515K
• ISSN：1528-7505

文摘

The slow diffusion reaction of octacyanometallate [Mo^V(CN)₈]^3–, lanthanide ions (Gd–Lu), and 1,10-phenanthroline (phen) in CH₃CN/H₂O has yielded eight isostructural one-dimensional chains, [Ln^III(phen)₂(H₂O)Mo^V(CN)₈]₂[(n-C₄H₉)₄N](NO₃)·2CH₃CN·4H₂O (Ln = Gd(1), Tb(2), Dy(3), Ho(4), Er(5), Tm(6), Yb(7), Lu(8)), in which [Ln^III(phen)₂(H₂O)]³⁺ and [Mo^V(CN)₈]^3– units are linked alternatively through cyanide groups, generating left- and right-handed helices. Interestingly, 1–8 undergo a resolvation–recrystallization process upon prolonging the diffusion-reaction time, together with the valence change from V to IV of Mo center and structural dimensionalities switching from helical chains to trinuclear clusters, (Hphen)_2.5[Ln^III_0.5(phen)(H₂O)][Mo^IV(CN)₈]·1.5CH₃CN (Ln = Gd(9), Tb(10), Dy(11), Ho(12), Er(13), Tm(14), Yb(15), Lu(16)). Magnetic studies of 1–16 revealed the typical effects induced by single-ion magnetic anisotropy and/or the population of low-lying excited states, and 11 and 13 showed extraordinary field-induced slow magnetic relaxations.