Chiral Metal–Organic Frameworks

Abstract

In the past two decades, metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) assembled from metal ions or clusters and organic linkers via metal–ligand coordination bonds have captivated significant scientific interest on account of their high crystallinity, exceptional porosity, and tunable pore size, high modularity, and diverse functionality. The opportunity to achieve functional porous materials by design with promising properties, unattainable for solid-state materials in general, distinguishes MOFs from other classes of materials, in particular, traditional porous materials such as activated carbon, silica, and zeolites, thereby leading to complementary properties. Scientists have conducted intense research in the production of chiral MOF (CMOF) materials for specific applications including but not limited to chiral recognition, separation, and catalysis since the discovery of the first functional CMOF (i.e., d- or l-POST-1). At present, CMOFs have become interdisciplinary between chirality chemistry, coordination chemistry, and material chemistry, which involve in many subjects including chemistry, physics, optics, medicine, pharmacology, biology, crystal engineering, environmental science, etc. In this review, we will systematically summarize the recent progress of CMOFs regarding design strategies, synthetic approaches, and cutting-edge applications. In particular, we will highlight the successful implementation of CMOFs in asymmetric catalysis, enantioselective separation, enantioselective recognition, and sensing. We envision that this review will provide readers a good understanding of CMOF chemistry and, more importantly, facilitate research endeavors for the rational design of multifunctional CMOFs and their industrial implementation.

Liquid crystal-templated chiral nanomaterials: from chiral plasmonics to circularly polarized luminescence

“…Moreover, many other liquid-crystalline phases 324,325 , such as 2D chiral smectics and 3D blue phases, and inorganic chiral photonic crystals 326 , can be applied for the development of chiral hierarchical nanomaterials with unprecedented functionalities. Chiral metal-organic frameworks (MOFs), as an emerging class of nanoporous chiral assemblies, could be one of the preeminent chiral template candidates due to their versatile performance in combination with diverse functional nanomaterials 327 . Owing to the arbitrary design capability, chiral functional nanomaterials can also be constructed with chiroptical properties that may not be readily revealed within their molecular counterparts, such as chirality-dependent mechanical properties 328 and magnetically induced chiroptical properties 329 .…”

Synthesis of a Chiral 3,6T22-Zn-MOF with a T-Shaped Bifunctional Pyrazole-Isophthalate Ligand Following the Principles of the Supramolecular Building Layer Approach

“…Overall, this work can be considered a starting point to obtain chiral and potentially porous MOFs using bifunctional and T-shaped pyrazole-carboxylate ligands. Chiral MOFs are promising materials for enantioselective adsorption, separation and catalysis [ 20 , 21 , 22 ].…”

“…Instead of the expected rtl -topology, which had been found for the MOFs rtl -[Cu(HIsa-az-dmpz)] and rtl -[Zn(HIsa-az-dmpz)] with the related HIsa-az-dmpz 2– linker [ 13 ], here, the rare chiral 3,6T22 -topology was obtained in [Zn(Isa-az-tmpz)]·~1–1.5 DMF through the reaction of Zn(NO 3 ) 2 ·4 H 2 O with the newly synthesized T-shaped pyrazole-carboxylate ligand Isa-az-tmpz 2– (5-(2-(1,3,5-trimethyl-1H-pyrazol-4-yl)azo)isophthalate). Chiral MOFs are of interest for chiral separation and catalysis [ 20 , 21 , 22 ].…”

Advances in the Structural Strategies of the Self-Assembly of Photoresponsive Supramolecular Systems

“…MOFs, also known as porous coordination polymers (PCPs), are assembled from metal ions or clusters and organic linkers via metal−ligand coordination bonds and have captivated significant scientific interest on account of their high crystallinity, exceptional porosity and tunable pore size, high modularity, and diverse functionality. However, to date, the potential of chiral MOF (CMOF) materials for specific applications include chiral recognition, separation technologies, and catalysis [ 71 ]. Regarding the above, the definition that has been best carried out for MOFs is the one that Barton and collaborators very accurately expose.…”