Polarization Engineering in Vinylene‐Linked COFs Toward Efficient Neuromorphic Computing

Functional delocalized covalent organic frameworks (COFs) show promise as active layers for the development of memristor switches and multistate functionalities. However, their potential is limited by poor electron mobility and suboptimal reaction kinetics. This study explores polarization engineering to modify the local electronic structure of the biaryl units within vinylene‐linked COFs. By implementing a conformation‐locking strategy that strategically enhances N + polarization and the redox activity of the framework, this design not only decreases the interfacial Schottky barrier but also facilitates efficient electron transfer, thereby promoting the delocalization of framework electrons, which modulates the conductive state in organic memristors. Furthermore, the polarization of ions, amplified by pyridine nitrogen nuclei and robust interlayer stacking, ensures effective counterion deintercalation and migration. The constructed Al/COF‐DIBPY/Au memristor exhibits a high analog on‐off current ratio (I max /I min = 15.7) under a 0.5 V drive. Utilizing these properties, the device shows great potential in performing speech emotion recognition tasks. When integrated into a convolutional neural network, it achieves a learning recognition accuracy of up to 95% in these tasks. This research offers novel insights into the construction of high‐efficiency neuromorphic computing devices based on polarization‐modulated COFs.