Chiral chemistry of metal–camphorate frameworks

Abstract

This critical review presents the various synthetic approaches and chiral chemistry of metal-camphorate frameworks (MCamFs), which are homochiral metal-organic frameworks (MOFs) constructed from a camphorate ligand. The interest in this unique subset of homochiral MOFs is derived from the many interesting chiral features for both materials and life sciences, such as asymmetrical synthesis or crystallization, homochiral structural design, chiral induction, absolute helical control and ligand handedness. Additionally, we discuss the potential applications of homochiral MCamFs. This review will be of interest to researchers attempting to design other homochiral MOFs and those engaged in the extension of MOFs for applications such as chiral recognition, enantiomer separation, asymmetric catalysis, nonlinear sensors and devices.

Chiral exploration of 6,12‐diphenyldibenzo[b,f][1,5]diazocine with stable conformation

“…Chirality plays a pivotal role in chemistry, medicine, biochemistry, and materials science . Classic chirality based on sp hybridized stereogenic centers has been well investigated, while less emphasis has been devoted to inherent chirality induced only by special molecular conformation.…”

“…Chirality plays a pivotal role in chemistry, medicine, biochemistry, and materials science. [1][2][3][4][5][6] Classic chirality based on sp 2 hybridized stereogenic centers has been well investigated, while less emphasis has been devoted to inherent chirality induced only by special molecular conformation. Recently, the concept of conformational chirality based on axial and planar chiral molecules has become a topic of intense interest.…”

Recent development trends for chiral stationary phases based on chitosan derivatives, cyclofructan derivatives and chiral porous materials in high performance liquid chromatography

“…As an inexpensive, commercially available multi‐dentate ligand, camphoric acid (H 2 cam) is a very good choice to explore chiral coordination chemistry . Since chiral MOFs constructed from D‐(+)‐camphoric acid exhibit excellent recognition ability and enantioselectivity as a stationary phase in GC, our group and the Liu group have taken several homochiral MOFs including [Cu 2 (D‐Cam) 2 (4,4′‐bipyridine)] n , [Zn 2 (D‐Cam) 2 (4,4′‐bipyridine)] n , [Co 2 (D‐cam) 2 (4,4′‐trimethylenedipyridine)], [Cd 2 (D‐Cam) 3 ]·2HDMA·4DMA and (Me 2 NH 2 ) 2 [Mn 4 O(D‐cam) 4 ]·(H 2 O) 5 constructed from D‐(+)‐camphoric acid and different metal ions as the stationary phases for HPLC separation .…”

“…Over the last few decades, porous solid materials such as metal-organic frameworks, covalent organic frameworks (COFs), porous organic frameworks, and porous organic cages have undergone explosive growth, and have attracted a great deal of attention from chemists, physicists, and materials scientists [71]. Among them, homochiral porous crystal materials have very promising applications in the fields of adsorption, enantioselective separation, asymmetric catalysis, and chiral sensors [5,[71][72][73][74][75][76][77][78][79][80][81][82][83][84][85][86].…”

A Cooperative Pillar–Template Strategy as a Generalized Synthetic Method for Flexible Homochiral Porous Frameworks

“…[4,5] One particular aspect that interests us is the difference in pillaring between homochiral layers and nonchiral layers.T he low-symmetry of chiral ligands leads to homochiral corrugated layers,quite unlike those formed from higher-symmetry aromatic ligands such as planar 1,4-benzenedicarboxylate.A sar esult, chiral layers can create new opportunities in terms of the type of ligands that can be used for pillaring.One striking success that illustrates this point is the pillaring of homochiral sinusoidal [Zn 2 (d-cam) 2 ]( d-H 2 Cam = d-camphoric acid) layers in an X-pillaring mode by the tetrapyridyl ligand 1,2,4,5-tetra(4-pyridyl)benzene (TPB). [4,5] One particular aspect that interests us is the difference in pillaring between homochiral layers and nonchiral layers.T he low-symmetry of chiral ligands leads to homochiral corrugated layers,quite unlike those formed from higher-symmetry aromatic ligands such as planar 1,4-benzenedicarboxylate.A sar esult, chiral layers can create new opportunities in terms of the type of ligands that can be used for pillaring.One striking success that illustrates this point is the pillaring of homochiral sinusoidal [Zn 2 (d-cam) 2 ]( d-H 2 Cam = d-camphoric acid) layers in an X-pillaring mode by the tetrapyridyl ligand 1,2,4,5-tetra(4-pyridyl)benzene (TPB).…”