Modular Construction of Vinylene-Linked Covalent Organic Frameworks with Tunable Emission for Tumor Visualization

Covalent organic frameworks (COFs) with ordered π structures are very promising in porous light-emitting materials. However, most of these COFs are either poor in luminescence or lack of water-stability. Herein, a series of isostructural D-A vinylene-linked COFs were constructed based a new D_2h symmetric linker 1,4-bis(4,6-dimethyl-1,3,5-triazin-2-yl)benzene (TMTA) with high crystallinity, comparative high surface area and excellent chemical/thermal stability. Impressively, their adsorption and luminescence wavelength vary with respect to the density of π-systems in the electron-donating group, which constitute the foundation for molecular engineering the luminescent properties of vinylene-linked COFs. The DFT calculations further established the relationship between the luminescence properties and the donor electronic structure. Moreover, one of representative COF named FZU-203 showed inspiring applications in bioimaging, which may further provide strategic guidance for the use of vinylene-linked COFs as fluorescent nanoprobes in non-invasive medical diagnosis and visualization therapy of tumors.