Knippen Katharina, Bredenkötter Björn, Kanschat Lisa, Kraft Maryana, Vermeyen Tom, Herrebout Wouter, Sugimoto Kunihisa, Bultinck Patrick, Volkmer Dirk
Institute of Physics, Chair of Solid State and Materials Science Augsburg University, Universitätsstrasse 1, 86159 Augsburg, Germany.
Departement of Chemistry, University of Antwerp, Campus Groenenborger, Groenenborgerlaan, 171 G.V.018, 2020 Antwerp, Belgium and Department of Chemistry, University of Ghent, Krijgslaan 281, S3, 9000 Ghent, Belgium.
Dalton Trans. 2020 Nov 17;49(44):15758-15768. doi: 10.1039/d0dt02847a.
In this work, we introduce the first enantiopure bistriazolate-based metal-organic framework, CFA-18 (Coordination Framework Augsburg-18), built from the R-enantiomer of 7,7,7',7'-tetramethyl-6,6',7,7'-tetrahydro-3H,3'H-5,5'-spirobi[indeno[5,6-d]-[1,2,3]triazole] (H2-spirta). The enantiopurity and absolute configuration of the new linker were confirmed by several chiroselective methods. Reacting H2-spirta in hot N,N-dimethylformamide (DMF) with manganese(ii) chloride gave CFA-18 as colorless crystals. The crystal structure with the composition [Mn2Cl2(spirta)(DMF)2] was solved using synchrotron single-crystal X-ray diffraction. CFA-18 shows a framework topology that is closely related to previously reported metal-azolate framework (MAF) structures in which the octahedrally coordinated manganese(ii) ions are triazolate moieties, and the chloride anions form crosslinked one-dimensional helical chains, giving rise to hexagonal channels. In contrast to MAFs crystallizing in the centrosymmetric space group R3[combining macron], the handedness of the helices found in CFA-18 is strictly uniform, leading to a homochiral framework that crystallizes in the trigonal crystal system within the chiral space group P3121 (no. 152).
在这项工作中，我们介绍了首个基于对映体纯双三唑盐的金属有机框架CFA - 18（奥格斯堡配位框架-18），它由7,7,7',7'-四甲基-6,6',7,7'-四氢-3H,3'H-5,5'-螺双[茚并[5,6-d]-[1,2,3]三唑]（H2-spirta）的R-对映体构建而成。通过几种手性选择方法确认了新连接体的对映体纯度和绝对构型。在热的N,N-二甲基甲酰胺（DMF）中使H2-spirta与氯化锰（II）反应，得到无色晶体CFA - 18。使用同步加速器单晶X射线衍射解析了组成为[Mn2Cl2(spirta)(DMF)2]的晶体结构。CFA - 18展现出一种框架拓扑结构，它与先前报道的金属唑盐框架（MAF）结构密切相关，其中八面体配位的锰（II）离子连接三唑盐部分，氯离子形成交联的一维螺旋链，产生六边形通道。与在中心对称空间群R3[macron]中结晶的MAF不同，在CFA - 18中发现的螺旋的手性是严格一致的，导致形成一种在三角晶系的手性空间群P3121（编号152）中结晶的纯手性框架。
