School of Physical Science and Technology, ShanghaiTech University, Shanghai, 201210, China.
Shanghai Key Laboratory of High-Resolution Electron Microscopy, ShanghaiTech University, Shanghai, 201210, China.
Nat Commun. 2023 Jul 14;14(1):4215. doi: 10.1038/s41467-023-39998-x.
The enolimine-ketoenamine tautomerism has been utilised to construct 2D covalent organic frameworks (COFs) with a higher level of chemical robustness and superior photoelectronic activity. However, it remains challenging to fully control the tautomeric states and correlate their tautomeric structure-photoelectronic properties due to the mobile equilibrium of proton transfer between two other atoms. We show that symmetry-asymmetry tautomerisation from diiminol to iminol/cis-ketoenamine can be stabilised and switched in a crystalline, porous, and dynamic 3D COF (dynaCOF-301) through concerted structural transformation and host-guest interactions upon removal and adaptive inclusion of various guest molecules. Specifically, the tautomeric dynaCOF-301 is constructed by linking the hydroquinone with a tetrahedral building block through imine linkages to form 7-fold interwoven diamondoid networks with 1D channels. Reversible framework deformation and ordering-disordering transition are determined from solvated to activated and hydrated phases, accompanied by solvatochromic and hydrochromic effects useful for rapid, steady, and visual naked-eye chemosensing.
烯醇亚胺-酮亚胺互变异构已被用于构建具有更高化学稳定性和优越光电活性的二维共价有机框架（COFs）。然而，由于质子在两个其他原子之间的转移处于动态平衡，因此要完全控制互变异构态并将其互变异构结构与光电性质相关联仍然具有挑战性。我们表明，通过协同结构转化和主客体相互作用，在去除和自适应包含各种客体分子时，可以在结晶、多孔和动态的 3D COF（dynaCOF-301）中稳定和切换二亚胺醇到亚氨基/顺式-酮亚胺的对称-不对称互变异构。具体而言，通过亚胺键将氢醌与四面体砌块连接起来，形成具有 1D 通道的 7 重交织的钻石状网络，从而构建了互变异构的 dynaCOF-301。从溶剂化到活化和水合相，可逆的框架变形和有序-无序转变是由溶剂化和水合相决定的，同时还伴随着溶剂变色和水变色效应，可用于快速、稳定和直观的肉眼化学传感。
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