Structural and Morphological Engineering of Benzothiadiazole-Based Covalent Organic Frameworks for Visible Light-Driven Oxidative Coupling of Amines.

Covalent organic frameworks (COFs) are appealing platforms for photocatalysts because of their structural diversity and adjustable optical band gaps. The construction of efficient COFs for heterogeneous photocatalysis of organic transformations is highly desirable. Herein, we constructed a photoactive COF containing benzothiadiazole and triazine (BTDA-TAPT), for which the morphology and crystallinity might be easily tuned by slight synthetic variation. To unveil the relationship of photocatalytic properties between the structure and morphology, analogous COFs were synthesized by precisely tailoring building blocks. Systematic investigations indicated that tuning the structure and morphology might greatly impact photoelectric properties. The BTDA-TAPT featuring ordered alignment and perfect crystalline nature was more beneficial for promoting charge transfer and separation, which exhibited superior photocatalytic activity for visible light-driven oxidative coupling of amines. Outcomes from this study reveal the intrinsic synergy effects between the structure and morphology of COFs for photocatalysis.