Organic Chemistry

Strained delta-stacked motifs of nanogridarenes achieved via Pd-PPh3-controlled diastereoselective C-H gridization

Authors

  • Linghai Xie Nanjing University of Posts and Telecommunications ,
  • Ying Wei Nanjing University of Posts and Telecommunications ,
  • Wei Huang Nanjing University of Posts and Telecommunications ,
  • Xiangping Wu 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. ,
  • Yongxia Wang 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 ,
  • Yue Sun 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. ,
  • Xue Du 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 ,
  • Yongxia Yan 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 ,
  • Chaoyang Dong 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 ,
  • Wenjing Shi 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 ,
  • Yuyu Liu 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 ,
  • Juan Song 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 ,
  • Lei YANG 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

Abstract

Strained nanogrids are the hybrids between nanogrids and nanorings with high strain like CPPs, offering state-of-the-art models and versatile nanobricks for advanced materials. Herein, we reported the unique blue-emitting strained triangle windmill-type nanogrids (TWGs) with π-interrupted backbones and delta-stacked motifs that have two diastereoisomers with different strains (cis-trans-TWG 15.60 kcal/mol, cis-cis-TWG 13.31 kcal/mol). They are synthesized by Pd-PPh3-assisted C-H gridization with size-selectivity of TWGs in 35 % yield and diastereoselectivity of cis-trans-TWG/cis-cis-TWG (80:20). Single-crystal X-ray diffraction and non-covalent index reveal both diastereoisomers exhibit the unique angle, bending, torsion as well as steric strains. Among those, torsion strain of cis-trans-TWG is much greater than that of cis-cis-TWG. Furthermore, strain-induced red shift of 25 nm in cis-trans-TWG than cis-cis-TWG was confirmed by TDDFT and photophysics charaterization. Interestingly, aggregates-induced emission switching and enhancement was observed in cis-trans-TWG skeleton with concentration from 10-5 to 10-1.

Content

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Supplementary material

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supporting information
Supplementary Methods Supplementary Note 1. The Calculation of strain energies of TWGs, SWGs-F and TWGs-Th Supplementary Note 2. Characteristics of C-H gridization Supplementary Note 3. Theoretical calculation datas of TWG-TS1 and TWG-TS2 Supplementary Note 4. The crystal data of single crystal of cis-trans-TWG and co-crystal of cis-cis-TWG and cis-trans-TWG. Supplementary Note 5. Strain and aggregates effects of TWGs. Supplementary Note 6. GC-MS, MALDI-TOF-MS and NMR spectra for all substrates and products. Supplementary Reference
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Single crystals
Single-crystal X-ray Diffraction ofstrained nanogrids