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Crystal engineering of a chiral crystalline sponge that enables absolute structure determination and enantiomeric separation

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journal contribution
posted on 2023-05-18, 15:07 authored by Deng ChenghuaDeng Chenghua, Bai-Qiao Song, Matteo LusiMatteo Lusi, Andrey BezrukovAndrey Bezrukov, Molly M. Haskins, Mei-Yan Gao, Yun-Lei Peng, Jian-Gong Ma, Peng Cheng, Soumya MukherjeeSoumya Mukherjee, MICHAEL ZAWOROTKOMICHAEL ZAWOROTKO

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(NO3)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4′-bipyridine (bipy) afforded a homochiral cationic diamondoid, dia, network, [Ni(S-IDEC)(bipy)(H2O)][NO3], CMOM-5. Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of CMOM-5 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, ee, values of 36.2−93.5%. The structural adaptability of CMOM-5 enabled eight enantiomer@CMOM-5 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 R-4P2B, S-4P2B, and R-MPE.

Funding

SYNergistic SORBents

European Research Council

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Crystal Engineering of Task-Specific Materials

Science Foundation Ireland

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Green Adsorbents for Clean Energy (GrACE)

Science Foundation Ireland

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Ionic Ultramicroporous Polymer Adsorbents for Energy-efficient Purification of Commodity Chemicals

Science Foundation Ireland

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History

Publication

Crystal Growth & Design

Publisher

American Chemical Society

Other Funding information

The authors gratefully acknowledge support from the Irish Research Council (IRCLA/2019/167), European Research Council (ADG 885695), and Science Foundation Ireland (13/RP/B2549 and 16/IA/4624). S.M. acknowledges an SFI-IRCPathway award (21/PATH-S/9454) from the Science Foundation Ireland.

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  • Bernal Institute

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  • Chemical Sciences

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