Related Experiment Video
Updated: Apr 11, 2026
Development of Heterogeneous Enantioselective Catalysts using Chiral Metal-Organic Frameworks MOFs
Published on: January 17, 2020
Site-selective valence isomerism as a unified electronic trigger for magnetism, chirality, and catalysis in
Jin-Huang Peng1, Haitao Zhang2,3, Zhenwei Wei1
1College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, China.
Abstract:
Valence modulation at metal nodes provides a fundamental route to couple electronic structure with functional properties in metal-organic frameworks (MOFs). Achieving precise and stimulus-independent control of metal oxidation states within an isostructural lattice remains a central challenge. Here we demonstrate valence isomerism in a Ni-carboxylate framework, Ni3(OH)2(Cam)2(H2O)4, by combining pH adjustment with vortex-driven stirring. This approach yields an isostructural pair consisting of a Ni(II) parent phase and a mixed-valence Ni(II)/Ni(III) analog, in which approximately 25% of the Ni centers are oxidized to low-spin Ni3+ selectively at the Ni(1) sites. Subtle valence reconfiguration reorganizes the intrachain interactions within the [Ni3(OH)2] chains, reinforcing ferrimagnetic order and enhancing net magnetization. Concomitantly, the short-wavelength circular dichroism signals invert, and the oxygen-evolution overpotential decreases by ~100 mV. These results establish valence isomerism as an electronic trigger that coherently couples magnetic, chiroptical and catalytic properties in MOFs, offering a general design principle for multifunctionality in reticular materials.
More Related Videos
07:14Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
06:53Author Spotlight: Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks
Published on: June 9, 2023
Related Concept Videos
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...
02:42Valence Bond Theory
02:30Chirality at Nitrogen, Phosphorus, and Sulfur
A consequence of chirality is the need for enantiomeric resolution. While this is theoretically possible for all...
02:52Stereoisomerism
Isomers are different chemical species that have the same chemical formula.
Transition metal complexes often exist as geometric isomers, in which the same atoms are connected through the same types of bonds but with differences in their orientation in space. Coordination complexes with two different ligands in the cis and trans positions from a ligand of interest form isomers. For example, the octahedral [Co(NH3)4Cl2]+ ion has two isomers (Figure 1) In the cis...
02:05Prochirality
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...