Department of Chemistry, National University of Singapore , 3 Science Drive 3, Singapore 117543, Singapore.
Institute of Materials Research and Engineering, A*STAR , 2 Fusionopolis Way, Innovis, Singapore 138634, Singapore.
J Am Chem Soc. 2017 Jul 5;139(26):8897-8904. doi: 10.1021/jacs.7b02696. Epub 2017 Jun 23.
Porous materials such as covalent organic frameworks (COFs) are good candidates for molecular sieves due to the chemical diversity of their building blocks, which allows fine-tuning of their chemical and physical properties by design. Tailored synthesis of inherently functional building blocks can generate framework materials with chemoresponsivity, leading to controllable functionalities such as switchable sorption and separation. Herein, we demonstrate a chemoselective, salicylideneanilines-based COF (SA-COF), which undergoes solvent-triggered tautomeric switching. This is unique compared to solid-state salicylideneanilines' counterpart, which typically requires high energy input such as photo or thermal activation to trigger the enol-keto tautomerisim and cis-trans isomerization. Accompanying the tautomerization, the ionic properties of the COF can be tuned reversibly, thus forming the basis of size-exclusion, selective ionic binding or chemoseparation in SA-COF demonstrated in this work.
多孔材料,如共价有机骨架(COFs),由于其构建块的化学多样性,是分子筛的良好候选材料,通过设计可以精细调整其化学和物理性质。固有功能构建块的定制合成可以生成具有化学响应性的框架材料,从而实现可控的功能,如可切换的吸附和分离。在此,我们展示了一种基于水杨醛苯胺的化学选择性 COF(SA-COF),它经历溶剂触发的互变异构开关。与固态水杨醛苯胺的对应物相比,这是独特的,后者通常需要高能量输入,如光或热激活,以触发烯醇-酮互变异构和顺反异构化。伴随着互变异构,COF 的离子性质可以可逆地调节,从而形成尺寸排除、选择性离子结合或化学分离的基础,这在本工作中得到了证明。