Shi Wen-Juan, Du Li-Yun, Yang Hong-Yun, Zhang Kun, Hou Lei, Wang Yao-Yu
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry & Materials Science, Northwest University , Xi'an 710127, P. R. China.
Department of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University , Shantou 515063, Guangdong, P. R. China.
Inorg Chem. 2017 Aug 21;56(16):10090-10098. doi: 10.1021/acs.inorgchem.7b01657. Epub 2017 Aug 10.
Three new coordination polymers, {[Mn(pzbtz)(Cl)(HO)]·4HO} (1), {Mn(pzbtz)(SO)(HO)]·3HO} (2), and {[Mn(pzbtz)(HO)]·1.5DMA·2HO} (3), have been solvothermally synthesized with MnCl/MnSO and a bitriazole ligand, 5'-(pyrazin-2-yl)-2H,4'H-3,3'-bi(1,2,4-triazole) (Hpzbtz), in different solvent systems. Hpzbtz shows different geometrical configurations and coordination modes, leading to the diverse three-dimensional (3D) frameworks of 1-3. Complex 1 contains the trinuclear Mn(tr)X (X = Cl or HO) clusters and reveals an unobserved (3,4,8)-connected sqc929 topological framework with two types of cages. Complex 2 is a new (3,4,6)-connected network based on dinuclear Mn(tr) clusters, and 3 shows an 8-connected bcu topology with a novel tetranuclear Mn(tr) cluster. Complexes 1 and 2 show antiferromagnetic properties, while 3 reveals spin-canting magnetic behavior with an uncommonly high T around 44 K. In addition, 1 also possesses good adsorption selectivity for CO over CH and N and an uncommon gate-opening phenomenon.
通过溶剂热法，以氯化锰/硫酸锰和双三唑配体5'-(吡嗪-2-基)-2H,4'H-3,3'-联(1,2,4-三唑)(Hpzbtz)在不同溶剂体系中合成了三种新型配位聚合物，{[Mn(pzbtz)(Cl)(H₂O)]·4H₂O} (1)、{[Mn(pzbtz)(SO₄)(H₂O)]·3H₂O} (2)和{[Mn(pzbtz)(H₂O)]·1.5DMA·2H₂O} (3)。Hpzbtz呈现出不同的几何构型和配位模式，导致1 - 3具有多样的三维(3D)框架。配合物1包含三核Mn(Ⅲ)X (X = Cl或H₂O)簇，并揭示了一种未观察到的(3,4,8)-连接的sqc929拓扑框架，带有两种类型的笼。配合物2是基于双核Mn(Ⅲ)簇的新型(3,4,6)-连接网络，配合物3呈现出具有新型四核Mn(Ⅲ)簇的8-连接bcu拓扑结构。配合物1和2表现出反铁磁性质，而配合物3在约44 K时呈现出具有异常高T的自旋倾斜磁行为。此外，配合物1对CO相对于CH₄和N₂还具有良好的吸附选择性以及罕见的门控开启现象。
