Abstract

Designing structural order in electronically active organic solids remains a great challenge in the field of materials chemistry. Now, 2D poly(arylene vinylene)s prepared as highly crystalline covalent organic frameworks (COFs) by base-catalyzed aldol condensation of trimethyltriazine with aromatic dialdehydes are reported. The synthesized polymers are highly emissive (quantum yield of up to 50 %), as commonly observed in their 1D analogues poly(phenylene vinylene)s. The inherent well-defined porosity (surface area ca. 1000 m2  g-1 , pore diameter ca. 11 Å for the terephthaldehyde derived COF-1) and 2D structure of these COFs also present a new set of properties and are likely responsible for the emission color, which is sensitive to the environment. COF-1 is highly hydrophilic and reveals a dramatic macroscopic structural reorganization that has not been previously observed in framework materials.

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