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一种用于绝对结构测定和对映体分离的手性晶体海绵的晶体工程。

Crystal Engineering of a Chiral Crystalline Sponge That Enables Absolute Structure Determination and Enantiomeric Separation.

作者信息

Deng Chenghua, Song Bai-Qiao, Lusi Matteo, Bezrukov Andrey A, Haskins Molly M, Gao Mei-Yan, Peng Yun-Lei, Ma Jian-Gong, Cheng Peng, Mukherjee Soumya, Zaworotko Michael J

机构信息

Bernal Institute, Department of Chemical Sciences, University of Limerick, Limerick V94 T9PX, Ireland.

Department of Chemistry and Key Laboratory of Advanced Energy Material Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.

出版信息

Cryst Growth Des. 2023 May 16;23(7):5211-5220. doi: 10.1021/acs.cgd.3c00446. eCollection 2023 Jul 5.

DOI:10.1021/acs.cgd.3c00446
PMID:37426545
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10326857/
Abstract

Chiral metal-organic materials (CMOMs), can offer molecular binding sites that mimic the enantioselectivity exhibited by biomolecules and are amenable to systematic fine-tuning of structure and properties. Herein, we report that the reaction of Ni(NO), -indoline-2-carboxylic acid (-IDECH), and 4,4'-bipyridine (bipy) afforded a homochiral cationic diamondoid, , network, [Ni(-IDEC)(bipy)(HO)][NO], . Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of adapted its pore structure to bind four guest molecules, 1-phenyl-1-butanol (1P1B), 4-phenyl-2-butanol (4P2B), 1-(4-methoxyphenyl)ethanol (MPE), and methyl mandelate (MM), making it an example of a chiral crystalline sponge (CCS). Chiral resolution experiments revealed enantiomeric excess, , values of 36.2-93.5%. The structural adaptability of enabled eight enantiomer@ crystal structures to be determined. The five ordered crystal structures revealed that host-guest hydrogen-bonding interactions are behind the observed enantioselectivity, three of which represent the first crystal structures determined of the ambient liquids -4P2B, S-4P2B, and -MPE.

摘要

手性金属有机材料(CMOMs)能够提供分子结合位点,这些位点可模拟生物分子所表现出的对映选择性,并且易于对结构和性质进行系统的微调。在此,我们报道了硝酸镍、吲哚 - 2 - 羧酸(-IDECH)和4,4'-联吡啶(bipy)反应生成了一种同手性阳离子类金刚石网络,[Ni(-IDEC)(bipy)(H₂O)][NO₃]。由通过联吡啶连接体交联的棒状构建块(RBBs)组成,活化形式的 使其孔结构适应以结合四种客体分子,1 - 苯基 - 1 - 丁醇(1P1B)、4 - 苯基 - 2 - 丁醇(4P2B)、1-(4 - 甲氧基苯基)乙醇(MPE)和扁桃酸甲酯(MM),使其成为手性晶体海绵(CCS)的一个例子。手性拆分实验显示对映体过量值为36.2 - 93.5%。 的结构适应性使得能够确定八个对映体@晶体结构。五个有序晶体结构表明,主客体氢键相互作用是观察到的对映选择性的原因之一,其中三个代表了首次确定的环境液体 -4P₂B、S - 4P₂B和 -MPE的晶体结构。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/d0be68402159/cg3c00446_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/4176d2cb3824/cg3c00446_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/d4c8759c748b/cg3c00446_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/d0be68402159/cg3c00446_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/4176d2cb3824/cg3c00446_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/d4c8759c748b/cg3c00446_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/9ed5/10326857/d0be68402159/cg3c00446_0003.jpg

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