Ion-Electron Coupling-Driven Redox Behavior in Metal-Organic Frameworks

Redox-active metal-organic frameworks (MOFs) have long been proposed as electronic transport platforms, yet the microscopic origin of their conductivity remains debated. A theoretical demonstration reveals charge transport in a Zn(pyrazole-naphthalene diimide (NDI)) MOF arising not from delocalized band-like states but from redox hopping between discrete linker sites. Using ab initio molecular dynamics simulations combined with electronic structure analysis, we established a direct link among electron injection, structural reorganization, and transport. Electron accumulation proceeds sequentially and site-selectively from imide and carbonyl groups of the NDI core progressively involving pyrazole N atoms at higher reduction states, through a hierarchy of redox-active sites. In contrast, Zn nodes remain essentially redox-inactive, which confirms their structural role. Density-of-states analysis corroborates a transport regime dominated by linker-centered states with evolving p-character upon reduction, resulting in dynamically reconfigured conduction networks. Real-time trajectories reveal anisotropic linker-to-linker electron transfer modulated by counterion coordination. This cooperative ion-electron regime emerges from potential energy surface collapse into a single low-barrier transition (ΔG^‡ ≈ 45 meV), where ionic and electronic motions evolve adiabatically on the same free-energy landscape. Elucidating redox conductivity in Zn(pyrazole-NDI) MOFs provides a theoretical framework for use in neuromorphic computing and related technologies.