Materials Chemistry

Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation

Authors

  • Linghai Xie Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Ying Wei Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Chunxiao Zhong Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Qian Peng Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Qiujing Bao Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Dongqing Lin Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Xinzhe Peng Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Hongjian Wang Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Xinming Hu Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • He Zhang Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Xue Du Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Bin Sun Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Kang Xiao Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China ,
  • Wei HUANG Centre for Molecular Systems and Organic Devices ([email protected]), Key Laboratory for Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China. & Frontiers Science Center for Flexible Electronics (FSCFE), MIIT Key Laboratory of Flexible Electronics (KLoFE), Northwestern Polytechnical University, Xi'an 710072, China.

Abstract

Organic science & technology (OST) become the frontier horizon after nanotechnology, information technology as well as biotechnology toward the era of consciousness. Organic nanogridarenes (ONGAs) are becoming robust nanoscaffolds for next-generation multifunctional/intelligent semiconductors with tunable cross-scale features. However, the prerequisite of trans-dimensional & intelligent design is to clarify the gridization rules for the discovery of the powerful molecular gridization protocols. Here, we report an efficient and multiselective Csp2-Csp3 gridization based on dual halogen bonding (X···π and X···S, X = Br, I) self-activated electrophilic substitution of halogenated electron-rich molecular blocks under supersonic conditions. Windmill-type nanogrids of cyclopenta[1,2-b:5,4-b']dithiophene (WG4) were obtained with the maximum path selectivity (96%), nanogrid-size selectivity (67%), site-selectivity (>99%) and moderate diastereoselectivity (WG4-1-6:WG4-2-6:WG4-3-6:WG4-4-6 =1:3.3:5.3:0), superior to the previous Friedel-Crafts gridization. Mechanistic studies have revealed the roles of XBs where the X···S bonding accelerates dehalogenation after electrophilic attack, and the X···π bonding leads to the multiselectivity of WG4. Impressively, C2-symmetric WG4-1-6 (21×21×15 Å) crystallizes into a Fd3̄c space group as the 16th pure organic molecules in CCDC library and hierarchically self-assemble into a complex 3D porous superstructure.

Content

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Supplementary material

Thumbnail image of Manuscript-SI-20220322.pdf
Multiselective gridization achieved by electrophilic C-X activation of dual halogen bonding cooperation
Supplementary Methods Supplementary Note 1. Gridization development. Supplementary Note 2. Structural characterization of WG4 Supplementary Note 3. Mechanistic investigations Supplementary Note 4. Hierarchical self-assembly Supplementary Note 5. NMR spectra for all substrates and products Supplementary References