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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 vinylen
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