中国科学院化学研究所王栋团队报道了不规则六边形平铺共价有机骨架的网状设计与合成。2025年3月24日出版的《美国化学会杂志》发表了这项成果。

在网状化学的指导下，该团队将III型不规则六角形平铺解构成D_2h+D_2h单体的组合，并首次成功合成了具有命中拓扑结构的具有这种平铺的二维COFs。通过调整晶体生长条件，课题组人员得到了一组网状异构体，COF-hit和COF-bex，它们具有不同的网状结构。采用粉末X射线衍射和高分辨率透射电镜对其拓扑结构进行了精确表征。COF-hit在高湿度条件下表现出出色的吸水能力。这种以不规则平铺为主题的COFs的合理设计，为丰富COFs的结构类型和拓扑变化，促进网状化学的发展开辟了新的途径。

据了解，网状化学极大地促进了框架材料的发展，但由于对不规则瓦片长度和角度的严格限制，具有不规则瓦片的共价有机框架（COFs）很少。

附：英文原文

Title: Reticular Design and Synthesis of Covalent Organic Frameworks with Irregular Hexagonal Tiling

Author: Hong Li, Xiao-Rui Ren, Yan Wang, Daliang Zhang, Zitao Wang, Lan-Ting Wei, Xin-Lan Wang, Dong Wang

Issue&Volume: March 24, 2025

Abstract: Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because of the strict constraints on irregular tile lengths and angles. Guided by reticular chemistry, we deconstructed type III irregular hexagonal tiling into a combination of D2h + D2h monomers and achieved the first successful synthesis of 2D COFs featuring such tiling with hit topology. By tuning the crystal growth conditions, we obtained a set of reticular isomers, COF-hit and COF-bex, with distinct reticular structures. Powder X-ray diffraction and high-resolution transmission electron microscopy were employed to precisely characterize their topology structures. COF-hit demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design of COFs using irregular tiling opens a new avenue to diversify the structural types and topological varieties of COFs and promote the development of reticular chemistry.

DOI: 10.1021/jacs.5c00494

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c00494