Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized. Zinc cations form 8-connected (8-c) penta-metallic secondary building units (SBUs), while cadmium cations form 4-c trimetallic SBUs. These SBUs are linked by 4-c -OEt and -OH ligands to form noninterpenetrated 4, 8-c zinc CMOFs (-OEt and -OH) and 2-fold interpenetrated 4-c diamondoid () cadmium CMOFs (-OEt and -OH), respectively. At a ligand concentration of 24 μM, H-OEt and H-OH showed negligible luminescent quenching by - and -hydrobenzoin (HB) enantiomers with Stern-Völmer constants of 29-89 M. In contrast, CMOFs displayed efficient quenching by HB enantiomers with Stern-Völmer constants of 583-1200 M, due to significant HB preconcentration in CMOF channels via favorable host-guest interactions between CMOF frameworks and HB molecules. The CMOFs demonstrated luminescence quenching selectivity for -HB over HB, with -OEt exhibiting the highest quenching ratio (()/()) of 1.624. This work highlights the potential of CMOFs in enantioselective sensing applications.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/acs.inorgchem.4c05575 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Homochiral BINOL-Based Metal-Organic Frameworks for Luminescence Sensing of Hydrobenzoin Enantiomers.
Inorg Chem
January 2025
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized.
View Article and Find Full Text PDFThe curious case of co-planarity in di-nuclear triel complexes: a density functional investigation.
Dalton Trans
January 2025
Computational and Theoretical Chemistry Group, Department of Chemistry & Centre for Advanced Studies in Chemistry, Panjab University, Chandigarh-160014, India.
Density functional investigation of intramolecular triel (Tr) bonding present in di-nuclear aryl complexes of group 13 elements having general formula [(Tr)Me(2,6-(X)CHO)] (Tr = B, Al, Ga, In & Tl and X = OMe, OEt, OH, OPh, NH, SH, Cl, F) has been performed. Conclusive evidence of the concurrent two σ-hole interaction has been provided by analysis of the Tr bond length, interaction energy (Δ), second order perturbation energy (), charge transfer (Δ), quantum theory of atom in molecules (QTAIM) and noncovalent interaction (NCI) plots for 12 complexes. The Tr bond length in the optimized geometry varies from 2.
View Article and Find Full Text PDFLinear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R-bpy)Re(CO)H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere.
Inorg Chem
October 2024
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Six rhenium hydride complexes, [(6,6'-R-bpy)Re(CO)H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO to form rhenium formate complexes of the type [(6,6'-R-bpy)Re(CO){OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted.
View Article and Find Full Text PDFControlling the Degree of Interpenetration in Chiral Three-Dimensional Covalent Organic Frameworks via Steric Tuning.
J Am Chem Soc
August 2024
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai 200240, P. R. China.
Network interpenetration plays a crucial role in functionalizing porous framework materials. However, controlling the degree of interpenetration in covalent organic frameworks (COFs) to influence their pore sizes, shapes, and functionalities still remains a significant challenge. Here, we demonstrate a steric tuning strategy to control the degree of COF interpenetration and modulate their physicochemical properties.
View Article and Find Full Text PDFTransforming patterned defects into dynamic poly-regional topographies in liquid crystal oligomers.
Mater Horiz
July 2024
Human Interactive Materials (HIM), Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, Groene Loper 3, Eindhoven 5612AE, The Netherlands.
We create high-aspect-ratio dynamic poly-regional surface topographies in a coating of a main-chain liquid crystal oligomer network (LCON). The topographies form at the topological defects in the director pattern organized in an array which are controlled by photopatterning of the alignment layer. The defect regions are activated by heat and/or light irradiation to form reversible topographic structures.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!