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

doi:10.1038/s41467-024-54235-9

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

Nat Commun. 2024 Nov 20;15(1):10026. doi: 10.1038/s41467-024-54235-9.

Authors

Miaomiao Xue^#¹, Lei Zhang^#¹, Xiao-Xin Li², Zihao Chen¹, Fangyuan Kang¹, Xiang Wang¹, Qiang Dong¹, Xin Wang¹, Chun-Sing Lee³, Ya-Qian Lan⁴, Qichun Zhang^{5

6}

Affiliations

¹ Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue 83, Kowloon, Hong Kong SAR, P. R. China.
² School of Chemistry, South China Normal University, Guangzhou, 510006, P. R. China.
³ Department of Chemistry, Center of Super-Diamond and Advanced Films (COSDAF) & Hong Kong Institute of Clean Energy (HKICE), City University of Hong Kong, Kowloon, Hong Kong SAR, P. R. China.
⁴ School of Chemistry, South China Normal University, Guangzhou, 510006, P. R. China. yqlan@m.scnu.edu.cn.
⁵ Department of Materials Science and Engineering, City University of Hong Kong, Tat Chee Avenue 83, Kowloon, Hong Kong SAR, P. R. China. qiczhang@cityu.edu.hk.
⁶ Department of Chemistry, Center of Super-Diamond and Advanced Films (COSDAF) & Hong Kong Institute of Clean Energy (HKICE), City University of Hong Kong, Kowloon, Hong Kong SAR, P. R. China. qiczhang@cityu.edu.hk.

^# Contributed equally.

PMID: 39567482
DOI: 10.1038/s41467-024-54235-9

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.

Abstract

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