Structural Elucidation of the Mechanism of Molecular Recognition in Chiral Crystalline Sponges

To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S‐mandelate)2(4,4′‐bipyridine)3](NO3)2, CMOM‐1S,...

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Bibliographic Details
Published in:Angewandte Chemie 2020-09, Vol.132 (40), p.17753-17759
Main Authors: Zhang, Shi‐Yuan, Fairen‐Jimenez, David, Zaworotko, Michael J.
Format: Article
Language:English
Subjects:
Adaptability
Binding sites
Carbon dioxide
Chemistry
chiral binding sites
chiral crystalline sponges
chiral metal–organic frameworks
chiral separation and resolution
Crystal structure
Crystallinity
Isomers
Metal-organic frameworks
molecular recognition
Pore size
Porosity
Porous materials
Recognition
Structural analysis
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Summary:To gain insight into chiral recognition in porous materials we have prepared a family of fourth generation chiral metal–organic frameworks (MOFs) that have rigid frameworks and adaptable (flexible) pores. The previously reported parent material, [Co2(S‐mandelate)2(4,4′‐bipyridine)3](NO3)2, CMOM‐1S, is a modular MOF; five new variants in which counterions (BF4−, CMOM‐2S) or mandelate ligands are substituted (2‐Cl, CMOM‐11R; 3‐Cl, CMOM‐21R; 4‐Cl, CMOM‐31R; 4‐CH3, CMOM‐41R) and the existing CF3SO3− variant CMOM‐3S are studied herein. Fine‐tuning of pore size, shape, and chemistry afforded a series of distinct host–guest binding sites with variable chiral separation properties with respect to three structural isomers of phenylpropanol. Structural analysis of the resulting crystalline sponge phases revealed that host–guest interactions, guest–guest interactions, and pore adaptability collectively determine chiral discrimination. The chiral recognition mechanism of a family of chiral metal–organic materials was investigated towards the resolution of three racemic mixtures of phenylpropanol. X‐ray single‐crystal analysis of host–guest interactions revealed the specific binding sites with shape complementarity between the guest molecules and the adaptable chiral cavity.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.202006438