Wayment Lacey J, Huang Shaofeng, Chen Hongxuan, Lei Zepeng, Ley Ashley, Lee Se-Hee, Zhang Wei
Department of Chemistry, University of Colorado Boulder, Boulder, CO, 80309, USA.
Department of Mechanical Engineering, University of Colorado Boulder, Boulder, CO, 80309, USA.
Angew Chem Int Ed Engl. 2024 Oct 14;63(42):e202410816. doi: 10.1002/anie.202410816. Epub 2024 Sep 5.
Covalent organic frameworks (COFs) have emerged as versatile materials with many applications, such as carbon capture, molecular separation, catalysis, and energy storage. Traditionally, flexible building blocks have been avoided due to their potential to disrupt ordered structures. Recent studies have demonstrated the intriguing properties and enhanced structural diversity achievable with flexible components by judicious selection of building blocks. This study presents a novel series of ionic COFs (ICOFs) consisting of tetraborate nodes and flexible linkers. These ICOFs use borohydrides to irreversibly deprotonate the alcohol monomers to achieve a high degree of polymerization. Structural analysis confirms the dia topologies. Reticulation is explored using various monomers and metal counterions. Also, these frameworks exhibit excellent stability in alcohols and coordinating solvents. The materials have been tested as single-ion conductive solid-state electrolytes. ICOF-203-Li displays one of the lowest activation energies reported for ion conduction. This tetraborate chemistry is anticipated to facilitate further structural diversity and functionality in crystalline polymers.
共价有机框架（COFs）已成为具有多种应用的多功能材料，如碳捕获、分子分离、催化和能量存储。传统上，由于柔性构建块可能破坏有序结构，人们一直避免使用它们。最近的研究表明，通过明智地选择构建块，柔性组件可实现有趣的特性并增强结构多样性。本研究展示了一系列由四硼酸盐节点和柔性连接体组成的新型离子共价有机框架（ICOFs）。这些ICOFs使用硼氢化物使醇单体不可逆地去质子化，以实现高度聚合。结构分析证实了双拓扑结构。使用各种单体和金属抗衡离子探索了网状结构。此外，这些框架在醇类和配位溶剂中表现出优异的稳定性。这些材料已作为单离子导电固态电解质进行了测试。ICOF-203-Li显示出报道的离子传导活化能中最低的之一。预计这种四硼酸盐化学将促进结晶聚合物中进一步的结构多样性和功能性。
