Thermally Induced Persistent Covalent-Organic Frameworks Radicals

Persistent covalent-organic framework (COF) radicals hold important applications in magnetics and spintronics; however, their facile synthesis remains a daunting challenge. Here, three p-phenylenediacetonitrile-based COFs (named CityU-4, CityU-5, and CityU-6) were synthesized. Upon heat treatment (250 °C for CityU-4 and CityU-5 or 220 °C for CityU-6), these frameworks were brought into their persistent radical forms (no obvious changes after at least one year), together with several observable factors, including color changes, red-shifted absorption, the appearance of electron spin resonance (ESR) signals, and detectable magnetic susceptibility. The theoretical simulation suggests that after heat treatment, lower total energy and nonzero spin density are two main factors to guarantee persistent COFs radicals and polarized spin distributions. This work provides an efficient method for the preparation of persistent COF radicals with promising potentials.