Wafer‐Scale Multidimensional‐Topology COFs for Highly Reliable Neuromorphic Electronics

ABSTRACT The rapid synthesis and scalable design strategies of high‐reliability multi‐dimensional and multi‐topological covalent organic frameworks (MDT COFs) are of great significance for meeting the diverse technological application requirements with highly differential specific demands, especially in neuromorphic electronics. Here, we introduce aniline into a sonochemical synthesis platform, where thermodynamic‐kinetic synergistic control expands topological diversity and substrate compatibility. We synthesized 37 COFs covering 1D to 3D, including 10 previously unreported frameworks. Relying on a parallel optimization strategy involving geometric‐electronic co‐engineering, a 3D TAPPFe‐Cu 3 COF‐based wafer‐scale memristor incorporating multiple metal and redox centers is designed and applied to shortest‐path optimization in the Shanghai metro network, exhibiting an 80.1% reduction in energy consumption, 78.6% faster synaptic weight reset, and a 9.36‐fold improvement in TDDB lifetime compared with state‐of‐the‐art COF‐based devices. This synthetic methodology and material design strategy provide a robust foundation for application‐tailored high‐reliability COFs, while opening new avenues for diversified utilization of MDT COFs.