Understanding precise structures of two-/three- dimensional (2D/3D) covalent organic polymers (COPs) through single-crystal X-ray diffraction (SCXRD) analysis is important. However, how to grow high-quality single crystals for 2D/3D COPs is of challenge due to poor reversibility and difficult self-correction of covalent bonds. In addition, the success of introducing tellurium into the backbone to construct 2D/3D COPs and obtaining their single crystals is rare. Here, utilizing the strategy that a heavy element (e.g., tellurium) can form dynamic linkages with a self-correction function, we develop a fast and universal method for growing large-sized single crystals (up to 500 µm) for 2D/3D COPs, especially for 2D COPs. Three 2D COPs and one 3D COP are harvested through dynamic -Te-O-P- bonds in two days, with structures clearly uncovered via the SCXRD analysis. These 2D/3D COPs also show promising photocatalytic activities (nearly 100% selectivity and 100% yield) in superoxide anion radical-mediated coupling of (arylmethyl)amines.

通过单晶 X 射线衍射 （SCXRD） 分析了解二维/三维 （2D/3D） 共价有机聚合物 （COP） 的精确结构非常重要。然而，由于可逆性差且共价键难以自校正，如何生长高质量的 2D/3D COPs 单晶是一个挑战。此外，将碲引入主链构建 2D/3D COP 并获得其单晶的成功是罕见的。在这里，利用重元素（例如碲）可以形成具有自我校正功能的动态键的策略，我们开发了一种快速通用的方法，用于生长 2D/3D COPs（尤其是 2D COPs）的大尺寸单晶（高达 500 μm）。在两天内通过动态 -Te-O-P- 键收获了三个 2D COP 和一个 3D COP，并通过 SCXRD 分析清楚地揭示了结构。这些 2D/3D COP 在超氧阴离子自由基介导的（芳基甲基）胺偶联中也显示出有希望的光催化活性（近 100% 的选择性和 100% 的产率）。