Chiral transfer amidst one-dimensional linear polymers and two-dimensional network covalent organic frameworks: Striking a fine balance between helicity and crystallinity
Xinlin Zha1,2,§, Mengjuan Zuo2,§, Guilin Xu2, Zhong Yan2, Haining You2, Yi Xiong2, Ying Liu2, Yingying Li2, Liyan Yang2, Ke Liu2, Mufang Li2, Tao Zhao1(), Dong Wang1,2()
College of Chemistry and Chemical Engineering, Donghua University, Shanghai 201620, China
Key Laboratory of Textile Fiber and Products, Ministry of Education, Wuhan Textile University, Wuhan 430200, China
§ Xinlin Zha and Mengjuan Zuo contributed equally to this work.
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In this study, several two-dimensional (2D) network β-ketoenamine-linked covalent organic frameworks (COFs) with unique mesoscopic helicity and ground-state chirality were transformed from one-dimensional imine-linked linear polymers constructed from purely achiral monomers via linker replacement processes. The crystallinity and helicity of the resulting 2D network COFs could be well balanced even though the whole transformation process involved the covalent bond breakage and reorganization.
Abstract
The current landscape of chiral covalent organic frameworks (COFs) predominantly centered on constructing asymmetric molecular-scale chirality, often introducing an inherent contradiction to the COF symmetry and limiting diversity. Herein, we overcome these challenges by achieving chiral transfer between one-dimensional (1D) imine linear polymers (LPs) and two-dimensional (2D) network β-ketoenamine COFs composed of achiral monomers. We successfully synthesize several 1D imine LPs with mesoscopic helical chirality, comprising achiral C2-symmetric terephthalaldehyde and diamine linkers in a chiral supramolecular transcription system. Leveraging the irreversible tautomerism mechanism within the linker replacement approach, terephthalaldehyde (TPA) units in these helical 1D LPs are substituted with C3-symmetric 1,3,5-triformylphloroglucinol (TP), yielding the corresponding 2D network β-ketoenamine COFs. Crystallinity and helicity of the resultant β-ketoenamine COFs intimately hinge on reaction conditions, including the aldehyde stoichiometry of Tp and TPA, as well as the quantity and concentration of the catalyst employed. Under optimized conditions, the nucleation and growth were precisely governed, achieving a harmonious equilibrium of crystallinity and helicity within the generated 2D network β-ketoenamine COFs, even with covalent bond rupture, recombination, and topological transition (from [C2 + C2] to [C3 + C2]). Impressively, the ground state chirality inherent to helical 1D LPs seamlessly transfers to helical 2D network β-ketoenamine COFs. This study not only offers new perspectives on the development of chiral functional COFs, but also provides fresh insights into the precise control of COFs' microscopic morphology.
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Zha X, Zuo M, Xu G, et al. Chiral transfer amidst one-dimensional linear polymers and two-dimensional network covalent organic frameworks: Striking a fine balance between helicity and crystallinity. Nano Research, 2024, 17(6): 5726-5734. https://doi.org/10.1007/s12274-024-6523-7
