近日，北京大学邹如强团队研究了单晶二维聚（亚芳基亚乙烯基）共价有机框架。相关论文发表在2026年1月20日出版的《自然-化学》杂志上。

亚乙烯基连接的二维共轭共价有机框架，即二维聚（亚芳基亚乙烯基），在（光）电子学、光催化和电化学领域具有广阔应用前景。然而，传统的溶剂热合成方法通常制备的二维聚（亚芳基亚乙烯基）结晶度较差或难以调控。

研究组提出一种曼尼希-消除反应策略，通过可逆的C=C键形成机制，将8种二维亚胺-共价有机框架转化为11种高结晶性二维聚（亚芳基亚乙烯基），实现了精确的结晶调控。该通用方法可制备具有蜂窝状、方形或Kagome晶格的稳定二维聚（亚芳基亚乙烯基），其比表面积高达~2000 m² g^-1，晶格失配耐受度可达3.5%。

高分辨透射电子显微镜与连续旋转电子衍射揭示了基于三苯基苯的2微米尺寸单晶二维聚（亚芳基亚乙烯基）具有分子级有序结构。研究表明结晶度对电荷传输具有深远影响：基于苯并三噻吩的二维聚（亚芳基亚乙烯基）的电荷迁移率比其无定形类似物或二维聚亚胺前驱体高出十倍。这项工作为制备高结晶性二维共轭聚合物材料并实现其稳定应用提供了一条普适性路径。

附：英文原文

Title: Towards single-crystalline two-dimensional poly(arylene vinylene) covalent organic frameworks

Author: Ghouse, Shaik, Guo, Ziang, Gmez-Valenzuela, Sergio, Mcke, David, Zhang, Bowen, Gao, Lei, Paasch, Silvia, Fu, Yubin, Huang, Chuanhui, Naisa, Chandrashekar, Brunner, Eike, Bonn, Mischa, Ruiz Delgado, M. Carmen, Sun, Junliang, Zou, Ruqiang, Kaiser, Ute, Wang, Mingchao, Feng, Xinliang

Issue&Volume: 2026-01-20

Abstract: Vinylene-linked two-dimensional (2D) conjugated covalent organic frameworks, or 2D poly(arylene vinylene)s (2D PAVs), are promising polymer semiconductors for (opto-)electronics, photocatalysis and electrochemistry. However, conventional solvothermal synthesis often produces 2D PAVs that are poorly crystalline or difficult to access. Here we introduce a Mannich-elimination strategy that converts 8 2D imine-covalent organic frameworks into 11 highly crystalline 2D PAVs though a reversible C=C bond formation mechanism enabling precise crystallization control. This versatile approach affords robust 2D PAVs with honeycomb, square or kagome lattices, specific surface area up to ～2,000m2g1 and lattice-mismatch tolerance up to 3.5%. High-resolution transmission electron microscopy and continuous rotation electron diffraction reveal molecular-level ordering in a 2-μm-sized triphenylbenzene-based single-crystalline 2D PAV. We demonstrate that crystallinity profoundly influences charge transport, with benzotrithiophene-based 2D PAVs exhibiting charge mobilities tenfold higher than their amorphous analogues or 2D polyimine precursors. This work establishes a general route to highly crystalline 2D conjugated polymer materials for robust applications.

DOI: 10.1038/s41557-025-02048-8

Source: https://www.nature.com/articles/s41557-025-02048-8