Module-Patterned Polymerization towards Crystalline 2D sp² -Carbon Covalent Organic Framework Semiconductors

Despite rapid progress over the past decade, most polycondensation systems even upon a small structural variation of the building units eventually result in amorphous polymers other than the desired crystalline covalent organic frameworks. This synthetic dilemma is a central and challenging issue of the field. Here we report a novel approach based on module-patterned polymerization to enable efficient and designed synthesis of crystalline porous polymeric frameworks. This strategy features a wide applicability to allow the use of various knots of different structures, enables polycondensation with diverse linkers, and develops a diversity of novel crystalline 2D polymers and frameworks, as demonstrated by using the C=C bond-formation polycondensation reaction. The new sp² -carbon frameworks are highly emissive and enable up-conversion luminescence, offer low band gap semiconductors with tunable band structures, and achieve ultrahigh charge mobilities close to theoretically predicted maxima.