Zhang Ren-Chun, Wang Jun-Jie, Yuan Bai-Qing, Zhang Jing-Chao, Zhou Ling, Wang Hai-Bin, Zhang Dao-Jun, An Yong-Lin
Key Laboratory of New Optoelectronic Functional Materials (Henan Province), College of Chemistry and Chemical Engineering, Anyang Normal University , Anyang, 455000, China.
College of Chemistry, Dalian University of Technology , Dalian 116024, China.
Inorg Chem. 2016 Nov 7;55(21):11593-11599. doi: 10.1021/acs.inorgchem.6b02121. Epub 2016 Oct 27.
The synthesis of chiral zeolites remains a significant challenge because the primary tetrahedral building units are achiral and weak interactions exist between the guest and host frameworks. Here, we present the syntheses and characterization of three new chiral zeolitic halides, [H(Dabco)]AgX (X = Br (1) or I (2), Dabco = 1,4-diazabicyclo[2.2.2]octane) and [H(Dabco)][(Dabco)AgI] (3). Compounds 1 and 2 are isostructural, containing a 4-connected zeolitic framework built up from 3-ring units, with high-charge [H(Dabco)] located in chiral cages. Compound 3 contains a similar zeolitic [AgI] framework to that of 2, but a [Ag(Dabco)] unit is incorporated in each 3-ring, with [H(Dabco)] located in channels. These frameworks are chiral, representing the first examples of chiral zeolitic halides. The chirality transference of the frameworks for 1 and 2 was attributed to the template effect of the chiral [H(Dabco)] through strong electrostatic interactions and multiple hydrogen-bond interactions. For compound 3, direct coordination interactions play important roles in the chirality transference from the chiral Dabco ligand to the framework.
手性沸石的合成仍然是一项重大挑战，因为主要的四面体结构单元是非手性的，且客体与主体骨架之间存在弱相互作用。在此，我们展示了三种新型手性沸石卤化物[H(Dabco)]AgX（X = Br (1) 或 I (2)，Dabco = 1,4 - 二氮杂双环[2.2.2]辛烷）和[H(Dabco)][(Dabco)AgI] (3)的合成及表征。化合物1和2是同构的，包含由3 - 环单元构建的4 - 连接沸石骨架，高电荷的[H(Dabco)]位于手性笼中。化合物3含有与2类似的沸石[AgI]骨架，但每个3 - 环中都并入了一个[Ag(Dabco)]单元，[H(Dabco)]位于通道中。这些骨架是手性的，代表了手性沸石卤化物的首例。化合物1和2骨架的手性转移归因于手性[H(Dabco)]通过强静电相互作用和多重氢键相互作用产生的模板效应。对于化合物3，直接配位相互作用在从手性Dabco配体到手性骨架的手性转移中起重要作用。
