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

• Published in: Journal of the American Chemical Society Vol. 139; no. 44
• Main Authors: 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.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society (ACS) 09.10.2017
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 0002-7863; 1520-5126

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; dobpdc4– = 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.