Growing large single crystals of two- or three-dimensional covalent organic polymers through unconventional Te-O-P linkages
Miaomiao Xue, Lei Zhang, Xiaoxin Li, Zihao Chen, Fangyuan Kang, Xiang Wang, Qiang Dong, Xin Wang, Chun‐Sing Lee, Ya‐Qian Lan, Qichun Zhang
Abstract
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. Understanding precise structures of two-/three- dimensional covalent organic polymers through single-crystal X-ray diffraction analysis is interesting however, to grow high-quality single crystals of these materials is challenging. Here, the authors incorporate tellurium into the backbones covalent organic polymers as a concise and fast method to grow large single crystals.