Homochiral metal-organic frameworks (HMOFs) are efficient materials for enantioselective adsorption. However, the combination of size selectivity and enantioselectivity is still a major challenge in the field of HMOFs. Herein, two enantiomorphic HMOFs built from predesigned proline-derived ligands are presented. Both of them show multiple homochiral features: they contain four different helical chains and three types of helical channels. Due to the size effect of the helical channels, each HMOF can enantioselectively adsorb methyl lactate with high ee. The results reveal a new approach toward size-dependent enantioselective separation of racemic compounds by using HMOFs built from inexpensive proline derivatives.
Ring size-dependent diastereoselective coordination of unsymmetrical diamines containing one azacyclic nitrogen and one exocyclic nitrogen to [(η-CMe)MCl] cores where M = Rh, Ir and [Ru(η-cymene)Cl] is reported herein. Total stereoselectivity was observed with the six- and seven-membered azacycles, whereas the five-derivative proved poorly selective. All complexes were active for transfer hydrogenation but showed no enantioselectivity with prochiral ketones.
Macao Institute of Materials Science and Engineering (MIMSE), MUST-SUDA Joint Research Center for Advanced Functional Materials, Macau University of Science and Technology, Taipa, Macao 999078, China.
Photodriven chiral catalysis is the combination of photocatalysis and chiral catalysis and is considered one of the cleanest and most efficient methods for the synthesis of chiral compounds or drugs. Furthermore, due to the potential metal contamination associated with most metal-based catalysts, metal-free chiral photocatalysts are ideal candidates. In this work, we demonstrate that metal-free chiral carbon dots (CDs) exhibit size-dependent enantioselective photocatalytic activity.
The modulation of the A adenosine receptor is a promising strategy in cancer (immuno) therapy, with AAR antagonists emerging as immune checkpoint inhibitors. Herein, we report a systematic assessment of the impact of (di- and mono-)halogenation at positions 7 and/or 8 on both AAR affinity and pharmacokinetic properties of a collection of AAR antagonists and its study with structure-based free energy perturbation simulations. Monohalogenation at position 8 produced potent AAR ligands irrespective of the nature of the halogen.
Department of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin, 300071, China.
Porosity is a fundamental property of metal-organic frameworks (MOFs). However, the role of the pore size has always been underestimated in MOF-based luminescent sensors for enantioselective sensing. The construction of isoreticular MOFs (IRMOFs) with variable pore sizes and the synergy between chirality and luminescence is challenging.
Key Laboratory of Functional Molecular Engineering of Guangdong Province, School of Chemistry and Chemical Engineering , South China University of Technology, Guangzhou , 510641 , P. R. China.
Metal-organic frameworks (MOFs) imbedded privileged molecular catalysts are of particular interest due to their higher catalytic activities derived from the MOFs pore/channel confinement effect, improved lifetime through eliminating intermolecular deactivation pathway, and the recyclability based on their heterogeneity. In this work, a 3D chiral metallosalen-based MOF [Cd(Cu(salen))(DMF)]·DMF·3HO (1) with a 1D open channel was synthesized and characterized by single-crystal X-ray diffraction and other physicochemical methods. Upon postsynthetic reduction modification with NaBH, the conversion from imino to amino group on salen cores of 1 generates the reduction product 2 with a more flexible chiral group and more alkaline backbone, meanwhile still maintaining the original porous framework.
