A Three-Dimensional sp~2 Carbon-Conjugated Covalent Organic Framework

摘要

A first example of an sp~2 carbon-conjugated three-dimensional (3D) covalent organic framework (COF) (BUCT-COF-4) is synthesized via the Knoevenagel condensation of the saddle-shaped aldehyde-substituted cyclooctatetrathiophene and 1,4-phenylenediacetonitrile. Ascribed to the extended π-conjugation and long-range ordered structures, BUCT-COF-4 displays high Hall electron mobility of 1.97 cm~2 V~(-1) s~(-1) at room temperature. After it is doped with iodine, the material not only exhibits an enhanced electron mobility up to 2.62 cm~2 V~(-1) s~(-1) in ambient air but also presents an unexpected metal-free ferromagnetic phase transition arising from the formation of aligned spins unidirectional across the whole sp~2 carbon-conjugated 3D framework. This is the first report of a ferromagnetic phenomenon in 3D COF materials, which would broaden promising applications and open a new frontier in COF materials.