Zick, Mary E. Lee, Jung-Hoon Gonzalez, Miguel, I Velasquez, Ever O. Uliana, Adam A. Kim, Jaehwan Long, Jeffrey R. Milner, Phillip J. 2024-01-19T15:31:18Z 2024-01-19T15:31:18Z 2021-10-21 2021-02-03 0002-7863 https://pubs.kist.re.kr/handle/201004/117418 Fluoroarenes are widely used in medicinal, agricultural, and materials chemistry, and yet their production remains a critical challenge in organic synthesis. Indeed, the nearly identical physical properties of these vital building blocks hinders their purification by traditional methods, such as flash chromatography or distillation. As a result, the Balz-Schiemann reaction is currently employed to prepare fluoroarenes instead of more atom-economical C-H fluorination reactions, which produce inseparable mixtures of regioisomers. Herein, we propose an alternative solution to this problem: the purification of mixtures of fluoroarenes using metal-organic frameworks (MOFs). Specifically, we demonstrate that controlling the interaction of fluoroarenes with adjacent coordinatively unsaturated Mg2+ centers within a MOF enables the separation of fluoroarene mixtures with unparalleled selectivities. Liquid-phase multicomponent equilibrium adsorption data and breakthrough measurements coupled with van der Waals-corrected density functional theory calculations reveal that the materials Mg-2(dobdc) (dobdc(4-) = 2,5-dioxidobenzene-1,4-dicarboxylate) and Mg-2(m-dobdc) (m-dobdc(4-) = 2,4-dioxidobenzene-1,5-dicarboxylate) are capable of separating the difluorobenzene isomers from one another. Additionally, these frameworks facilitate the separations of fluoroanisoles, fluorotoluenes, and fluorochlorobenzenes. In addition to enabling currently unfeasible separations for the production of fluoroarenes, our results suggest that carefully controlling the interaction of isomers with not one but two strong binding sites within a MOF provides a general strategy for achieving challenging liquid-phase separations. English AMER CHEMICAL SOC STATIONARY-PHASE Fluoroarene Separations in Metal-Organic Frameworks with Two Proximal Mg2+ Coordination Sites Article 10.1021/jacs.0c11530 1 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.143, no.4, pp.1948 - 1958 JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 143 4 1948 1958 scie scopus 000618171900032 2-s2.0-85100657941 Chemistry, Multidisciplinary Chemistry Article STATIONARY-PHASE