Halogen hydrogen-bonded organic framework (XHOF) constructed by singlet open-shell diradical for efficient photoreduction of U(VI)

• Published in: Nature communications Vol. 13; no. 1; pp. 1389 - 9
• Main Authors: Feng, Lijuan, Yuan, Yihui, Yan, Bingjie, Feng, Tiantian, Jian, Yaping, Zhang, Jiacheng, Sun, Wenyan, Lin, Ke, Luo, Guangsheng, Wang, Ning
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 16.03.2022; Nature Publishing Group; Nature Portfolio
• Subjects: 140/131; 140/146; 140/58; 147/135; 639/301/923/1028; 639/638/298/923/1028; 639/638/298/923/3931; Bonding strength; Covalent bonds; Crystal structure; Crystallinity; Humanities and Social Sciences; Hydrogen; Hydrogen bonding; Hydrogen bonds; Immobilization; Ions; Irradiation; Ligands; Light irradiation; multidisciplinary; Photoreduction; Radiation; Science; Science (multidisciplinary); Uranium
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-022-29107-9

Synthesis of framework materials possessing specific spatial structures or containing functional ligands has attracted tremendous attention. Herein, a halogen hydrogen-bonded organic framework (XHOF) is fabricated by using Cl − ions as central connection nodes to connect organic ligands, 7,7,8,8-tetraaminoquinodimethane (TAQ), by forming a Cl − ···H 3 hydrogen bond structure. Unlike metallic node-linked MOFs, covalent bond-linked COFs, and intermolecular hydrogen bond-linked HOFs, XHOFs represent a different kind of crystalline framework. The electron-withdrawing effect of Cl − combined with the electron-rich property of the organic ligand TAQ strengthens the hydrogen bonds and endows XHOF-TAQ with high stability. Due to the production of excited electrons by TAQ under light irradiation, XHOF-TAQ can efficiently catalyze the reduction of soluble U(VI) to insoluble U(IV) with a capacity of 1708 mg-U g −1 -material. This study fabricates a material for uranium immobilization for the sustainability of the environment and opens up a new direction for synthesizing crystalline framework materials. While hydrogen bonded organic frameworks are well covered in the scientific literature, halogen hydrogen-bonded organic framework (XHOF) remain less explored. Here, the authors demonstrate a highly stable diradical-based XHOF and demonstrate photoreduction of uranyl ions and high capacity of uranyl immobilization.