Zhu Wen-Hua, Xiong Xia, Gao Chen, Li Shan, Zhang Yan, Wang Juan, Zhang Chi, Powell Annie K, Gao Song
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, PR China.
Dalton Trans. 2017 Oct 24;46(41):14114-14121. doi: 10.1039/c7dt02736b.
A series of isostructural lanthanide one-dimensional (1D) chain complexes, [Ln(INNO)(Bza)(HO)]·(HO) {INNO = isonicotinate N-oxide, Bza = benzoic acid; Nd(1), Eu(2), Gd(3), Tb(4), Dy(5), Er(6) and Y(7)}, have been successfully isolated by hydrothermal reactions utilizing two distinct carboxylates as co-ligands. Due to the similar steric hindrance of the two carboxylic ligands, the neighboring lanthanide ions are bridged simultaneously by their carboxyl groups from the opposite sides to form a 1D chain structure. The shape analysis of the eight-coordinated Dy analogue 5 highlights the coordination geometry of the distorted square antiprism (D). The solid-state luminescence of 2 and 4 was characterized. The static magnetic analysis of the Gd analogue 3 is indicative of the dominant weak intrachain antiferromagnetic interactions via the carboxylic ligands. Dynamic magnetic measurements for 5 revealed clear slow magnetic relaxation behaviour typical for single-molecule magnets (SMMs). Compound 5 represents a very rare example, reported as a mixed carboxylate bridged lanthanide SMM.
通过水热反应，利用两种不同的羧酸盐作为共配体，成功分离出一系列同构的镧系一维（1D）链状配合物，[Ln(INNO)(Bza)(H₂O)]·(H₂O) {INNO = 异烟酸N-氧化物，Bza = 苯甲酸；Nd(1)、Eu(2)、Gd(3)、Tb(4)、Dy(5)、Er(6) 和 Y(7)}。由于两种羧酸配体的空间位阻相似，相邻的镧系离子通过它们来自相反侧的羧基同时桥连，形成一维链结构。八配位Dy类似物5的形状分析突出了扭曲的四方反棱柱（D）的配位几何形状。对2和4进行了固态发光表征。Gd类似物3的静态磁性分析表明通过羧酸配体存在主要的弱链内反铁磁相互作用。对5的动态磁性测量揭示了单分子磁体（SMM）典型的明显慢磁弛豫行为。化合物5代表了一个非常罕见的例子，被报道为混合羧酸盐桥连的镧系SMM。
