1352730-33-6Relevant articles and documents
Thermolabile Cross-Linkers for Templating Precise Multicomponent Metal-Organic Framework Pores
Geary, Jackson,Wong, Andy H.,Xiao, Dianne J.
, p. 10317 - 10323 (2021)
While a number of approaches toward multicomponent metal-organic frameworks have been reported, new strategies affording greater structural versatility and molecular precision are needed to replicate the sophisticated active sites found in enzymes. Here, we outline a general method for templating functional groups within framework pores using thermolabile ligand cross-linkers. We show that tertiary ester-based cross-linkers can be used to install well-defined carboxylic acid pairs at precise relative distances and orientations. The tertiary ester linkages remain intact during framework formation but are readily cleaved to reveal free carboxylic acids upon microwave heating. Successful cross-linker synthesis, framework incorporation, and thermolysis is demonstrated using the mesoporous, terphenyl expanded analogues of MOF-74. When short cross-linkers are used, modeling studies show that the carboxylic acids are installed in a single configuration down the pore channels, spaced ~7 ? apart. These precisely positioned acid pairs can be used as synthetic handles to build up more complex cooperative active sites.
Separation of Xylene Isomers through Multiple Metal Site Interactions in Metal-Organic Frameworks
Gonzalez, Miguel I.,Kapelewski, Matthew T.,Bloch, Eric D.,Milner, Phillip J.,Reed, Douglas A.,Hudson, Matthew R.,Mason, Jarad A.,Barin, Gokhan,Brown, Craig M.,Long, Jeffrey R.
, p. 3412 - 3422 (2018)
Purification of the C8 alkylaromatics o-xylene, m-xylene, p-xylene, and ethylbenzene remains among the most challenging industrial separations, due to the similar shapes, boiling points, and polarities of these molecules. Herein, we report the evaluation of the metal-organic frameworks Co2(dobdc) (dobdc4- = 2,5-dioxido-1,4-benzenedicarboxylate) and Co2(m-dobdc) (m-dobdc4- = 4,6-dioxido-1,3-benzenedicarboxylate) for the separation of xylene isomers using single-component adsorption isotherms and multicomponent breakthrough measurements. Remarkably, Co2(dobdc) distinguishes among all four molecules, with binding affinities that follow the trend o-xylene > ethylbenzene > m-xylene > p-xylene. Multicomponent liquid-phase adsorption measurements further demonstrate that Co2(dobdc) maintains this selectivity over a wide range of concentrations. Structural characterization by single-crystal X-ray diffraction reveals that both frameworks facilitate the separation through the extent of interaction between each C8 guest molecule with two adjacent cobalt(II) centers, as well as the ability of each isomer to pack within the framework pores. Moreover, counter to the presumed rigidity of the M2(dobdc) structure, Co2(dobdc) exhibits an unexpected structural distortion in the presence of either o-xylene or ethylbenzene that enables the accommodation of additional guest molecules.