Construction of Luminescent Three‐Dimensional Covalent Organic Frameworks for Molecular Decoding of Wide Organic Compounds.

Constructing highly conjugated three‐dimensional covalent organic frameworks (3D COFs), particularly those with luminescent features, remains a significant challenge. In this work, we successfully synthesized a 3D COF, named 3D‐Py‐SP‐COF, using a rigid and orthogonal spirobifluorene building block for the spatial 3D structure construction and planar pyrene as luminescent units. The incorporation of the pyrene and the unique rigid 3D network structure endow 3D‐Py‐SP‐COF with fluorescent properties. The successful formation of this 3D COF was verified by FT‐IR, solid‐state 13C CP‐MAS NMR. Structural simulations based on the experimental powder X‐ray diffraction analysis revealed that 3D‐Py‐SP‐COF adopted a two‐fold interpenetrated pts topology. The highly conjugated porous framework and fluorescent nature allow precise detection and localization of more than two dozen volatile organic compounds (VOCs), including aromatics, alcohols, and other commonly encountered industrial VOCs. [ABSTRACT FROM AUTHOR]