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<p>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, Ni<sub>3</sub>(OH)<sub>2</sub>(Cam)<sub>2</sub>(H<sub>2</sub>O)<sub>4</sub>, 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 Ni<sup>3+</sup> selectively at the Ni(1) sites. Subtle valence reconfiguration reorganizes the intrachain interactions within the [Ni<sub>3</sub>(OH)<sub>2</sub>] 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.</p>

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Site-selective valence isomerism as a unified electronic trigger for magnetism, chirality, and catalysis in Ni–carboxylate MOFs

  • 期刊论文

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  • 发表日期：

    2026年4月9日

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  • Jin-Huang Peng,
  • Haitao Zhang,
  • Zhenwei Wei,
  • Yang Cao,
  • Jun Zhang

摘要

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.