Enantioselective Inclusion of Alcohols by Solvent-Controlled Assembled Flexible Metal–Organic Frameworks

Abstract

Through judicious choice of the ligands and patient regulation of the solvent conditions, three unique chiral coordination polymeric isomers have been synthesized. Their structures, gas adsorption, and structural interconversion have been studied. One of the isomers displays dynamic behavior, and its use in the enantioselective separation of chiral alcohols has also been reported.

Structural Insight into Guest Binding Sites in a Porous Homochiral Metal–Organic Material

“…Nevertheless, to our knowledge this performance is 1.7 times higher than that reported for any other porous MOM. 12 Further experiments were conducted at 40 °C for 1 day (Table S4), and the ee values were observed to improve gradually as the MeOH/H 2 O ratio was increased. However, once again the loading of PP dropped, this time from 98% to 28%.…”

“…15 In most instances, much lower ee values are observed. [10][11][12]14 Whereas the development of CMOMs in terms of network design and functionalization has been well-addressed, 13,19 the nature of the interactions that promote enantioselective separation by CMOMs has been understudied. Simply put, the combination of porosity and chirality is not on its own enough to enable strong enantioselectivity.…”

“…The most typical approach to generate CMOMs involves homochiral molecular building blocks (MBBs) as opposed to relying upon spontaneous resolution of CMOMs sustained by achiral MBBs . CMOMs with homochiral MBBs covalently bonded to the framework as linking or pendant ligands have been synthesized using a variety of ligands, including l -aspartate, l -lactate, l -alanine derivatives, l -leucine derivatives, l -camphorate derivatives, d -tartrate derivatives, BINOL derivatives, and Schiff base derivatives . However, the relative cost of homochiral species and racemization during synthesis have limited the development of CMOMs relative to MOMs in general .…”

Crystal structure of an organic–inorganic supramolecular salt based on a 4,4′-methylenebis(3,5-dimethyl-1H-pyrazol-2-ium) cation and a β-octamolybdate anion

“…The considerable steric hindrance imposed by the two peripheral 3,5-dimethyl-1Hpyrazol-2-ium moieties induces a tetrahedral angle of the bridging methylene group of 113.56 17, which is very close to the median value found in similar structures (from the CSD: median of 114.7 from 109 hits with range of 111.0-120.0 ). Conversely, the dihedral angle subtended by these two peripheral moieties is significantly more dependent on the crystal structure itself, with the literature values (from 109 hits in the CSD) ranging from as low as 55.1 (a chiral coordination polymer with Cu 2+ described by Lin et al, 2014) to 90.0 (an Ni 2+ layered network described by Goswami et al, 2013). Nevertheless, the interplanar angle registered for the title compound, 77.85 15 14Å range].…”

Preparation and characterization of Ni2(mal)2(bpy) homochiral MOF membrane

“…Homochiral metal‐organic frameworks (HMOFs), as an important subclass of MOF materials, were commonly synthesized by involving chiral building blocks or templates . Some HMOFs with unusual integration of absolute helicity, molecular chirality, and three‐dimensional intrinsic chiral net demonstrate some attractive properties, such as enantioselective adsorption, chiral catalysts, and CO 2 capture …”