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Growing large single crystals of two- or three-dimensional covalent organic polymers through unconventional Te-O-P linkages

  • Miaomiao Xue,
  • Lei Zhang,
  • Xiao-Xin Li,
  • Zihao Chen,
  • Fangyuan Kang,
  • Xiang Wang,
  • Qiang Dong,
  • Xin Wang,
  • Chun-Sing Lee,
  • Ya-Qian Lan,
  • Qichun Zhang

摘要

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.