Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal–Organic Framework

Martell, Jeffrey D.; Porter-Zasada, Leo B.; Forse, Alexander C.; Siegelman, Rebecca L.; Gonzalez, Miguel I.; Oktawiec, Julia; Runčevski, Tomče; Xu, Jiawei; Srebro-Hooper, Monika; Milner, Phillip J.; Colwell, Kristen A.; Autschbach, Jochen; Reimer, Jeffrey A.; Long, Jeffrey R.

doi:10.1021/jacs.7b09983

Title: Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal–Organic Framework

Journal Article · Mon Oct 09 00:00:00 EDT 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.7b09983· OSTI ID:1464156

Martell, Jeffrey D. ^[1]; Porter-Zasada, Leo B. ^[2];

^[3]; Siegelman, Rebecca L. ^[2]; Gonzalez, Miguel I. ^[2]; Oktawiec, Julia ^[2]; Runčevski, Tomče ^[4]; Xu, Jiawei ^[5];

^[6]; Milner, Phillip J. ^[2]; Colwell, Kristen A. ^[7];

^[8]; Reimer, Jeffrey A. ^[9];

^[10]

Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Miller Inst. for Basic Research in Science
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering. Berkeley Energy and Climate Inst.
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Jasco Corporation, Hachioji (Japan)
Jagiellonian Univ., Krakow (Poland). Faculty of Chemistry
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Univ. at Buffalo, NY (United States). Dept. of Chemistry
Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Univ. of California, Berkeley, CA (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division

Chiral metal–organic frameworks have attracted interest for enantioselective separations and catalysis because of their high crystallinity and pores with tunable shapes, sizes, and chemical environments. Chiral frameworks of the type M₂(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc^4– = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) seem particularly promising for potential applications because of their excellent stability, high internal surface areas, and strongly polarizing open metal coordination sites within the channels, but to date these materials have been isolated only in racemic form. In this paper, we demonstrate that when appended with the chiral diamine trans-1,2-diaminocyclohexane (dach), Mg₂(dobpdc) adsorbs carbon dioxide cooperatively to form ammonium carbamate chains, and the thermodynamics of CO₂ capture are strongly influenced by enantioselective interactions within the chiral pores of the framework. We further show that it is possible to access both enantiomers of Mg₂(dobpdc) with high enantiopurity (≥90%) via framework synthesis in the presence of varying quantities of d-panthenol, an inexpensive chiral induction agent. Investigation of dach–M₂(dobpdc) samples following CO₂ adsorption—using single-crystal and powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory calculations—revealed that the ammonium carbamate chains interact extensively with each other and with the chiral M₂(dobpdc) pore walls. Finally, subtle differences in the non-covalent interactions accessible in each diastereomeric phase dramatically impact the thermodynamics of CO₂ adsorption.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Advanced Research Projects Agency - Energy (ARPA-E); National Inst. of Health (NIH) (United States); National Science Foundation (NSF)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; SC0001015; AR0000402; S10OD023532; GM120799; CHE-1560881

OSTI ID:: 1464156

Journal Information:: Journal of the American Chemical Society, Vol. 139, Issue 44; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 74 works

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