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May 2, 20261 citations

Guest-Triggered Charge Transfer for Magnetic Change in Redox-Active MOF Magnets.

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JZJun ZhangYCYang CaoWKWataru Kosaka

Key Points

  • This Account investigates how guest-induced charge transfer influences magnetic properties in redox-active metal-organic frameworks (MOFs).
  • Developed two mechanisms for magnetic switching: on-host charge transfer and host-guest charge transfer.
  • Positioned donor-acceptor pairs for electronic instability.
  • Identified five systems demonstrating guest-induced on-host charge transfer.
  • Successful guest-induced magnetic switching was achieved in multiple candidate frameworks.
  • On-host charge transfer mechanism showed promise with neutral guests affecting electronic states.
  • Strategies outlined could lead to advancements in multifunctional materials with unique electronic properties.

Abstract

A frameworks that support multiple, closely spaced electronic states. Because these states lie in delicate energetic balance, subtle structural perturbations such as guest adsorption can trigger charge transfer and reorganize magnetic ground states. To enable guest-induced magnetic switching, we have developed two key mechanisms: (1) on-host charge transfer (CT), where neutral guests modulate the electronic state of the host framework, and (2) host-guest CT, where redox-active guests directly exchange electrons with the framework. Whereas host-guest CT is limited to strongly redox-active guests, on-host CT exploits the intrinsic energetic competition between donor and acceptor units, amplified by lattice electrostatics. The central question addressed in this Account is how to rationally design D/A-MOFs poised at electronic instability, such that minor external stimuli can tip the balance between competing charge states. We outline two guiding strategies: positioning donor-acceptor pairs at the boundary of multiple electronic states and targeting systems that display emergent electronic configurations beyond initial predictions. Guided by these principles, five representative systems showing guest-induced on-host CT have been discovered. We hope this Account will encourage continued investigation into these multifunctional materials at the interface of magnetism, electronic regulation, and host-guest chemistry.

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Cite This Study

Zhang et al. (2026) studied this question.

synapsesocial.com/papers/69f5945c71405d493afff271https://doi.org/10.1021/acs.accounts.6c00023
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