Transforming 2D Imine into 3D Thiazole Covalent Organic Frameworks by Conjugated Connectors: Fully Conjugated Photocatalysts.

We developed a robust three-dimensional (3D) covalent organic framework (COF), fully conjugated in both the planar (x, y) and interlayer (z) directions, using a one-pot sulfurization process. We converted the two-dimensional (2D) imine-linked COF (Py-BDA-COF) to the 3D thiazole-linked COF (3D-Py-BDA-S-COF). In the interlayer direction (z-axis), the alternating covalently bound acetylene and ethylene arrangements serve as conjugated connectors ("pillars") and create a fully conjugated and very robust COF in all three dimensions. On top of this, the presence of the sulfur lone pair electrons in the thiazole rings considerably enhances the electron delocalization degree of the frameworks. The 3D-Py-BDA-S-COF is successfully evaluated in the photocatalytic reduction of nitrobenzene.