Vinylene‐Linked Covalent Organic Frameworks (COFs) with Symmetry‐Tuned Polarity and Photocatalytic Activity

The polarity of a semiconducting molecule affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D3h -symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene-linked covalent organic framework (g-C54 N6 -COF) via Knoevenagel condensation with another D3h -symmetric monomer 2,4,6-tris(4'-formyl-biphenyl-4-yl)-1,3,5-triazine. Replacing tricyanomesitylene with a C2v -symmetric 3,5-dicyano-2,4,6-trimethylpyridine gave a less-symmetric vinylene-linked COF (g-C52 N6 -COF). The octupolar conjugated characters of g-C54 N6 -COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behavior as compared with g-C52 N6 -COF, such as enhanced light-harvesting and excellent photo-induced charge generation and separation. Along with the matched energy level, g-C54 N6 -COF enabled the two-half reactions of photocatalytic water splitting with an average O2 evolution rate of 51.0 μmol h-1 g-1 and H2 evolution rate of 2518.9 μmol h-1 g-1 . Such values are among the highest of state-of-the-art COF photocatalysts.