Selective Synthesis of Conjugated Chiral Macrocycles: Sidewall Segments of (-)/(+)-(12,4) Carbon Nanotubes with Strong Circularly Polarized Luminescence

Jinyi Wang; Guilin Zhuang; Muqing Chen; Dapeng Lu; Zhe Li; Qiang Huang; Hongxing Jia; Shengsheng Cui; Xiang Shao; Shangfeng Yang; Pingwu Du

doi:10.1002/anie.201909401

Selective Synthesis of Conjugated Chiral Macrocycles: Sidewall Segments of (-)/(+)-(12,4) Carbon Nanotubes with Strong Circularly Polarized Luminescence

Angew Chem Int Ed Engl. 2020 Jan 20;59(4):1619-1626. doi: 10.1002/anie.201909401. Epub 2019 Dec 4.

Authors

Affiliations

¹ Hefei National Laboratory for Physical Sciences at the Microscale, CAS Key Laboratory of Materials for Energy Conversion, Department of Materials Science and Engineering, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), University of Science and Technology of China, Hefei, Anhui Province, 230026, China.
² College of Chemical Engineering, Zhejiang University of Technology, 18, Chaowang Road, Hangzhou, Zhejiang Province, 310032, China.
³ Department of Chemical Physics, Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui Province, 230026, China.

PMID: 31710148
DOI: 10.1002/anie.201909401

Abstract

Carbon nanotubes (CNTs) have unusual physical properties that are valuable for nanotechnology and electronics, but the chemical synthesis of chirality- and diameter-specific CNTs and π-conjugated CNT segments is still a great challenge. Reported here are the selective syntheses, isolations, characterizations, and photophysical properties of two novel chiral conjugated macrocycles ([4]cyclo-2,6-anthracene; [4]CAn_2,6 ), as (-)/(+)-(12,4) carbon nanotube segments. These conjugated macrocyclic molecules were obtained using a bottom-up assembly approach and subsequent reductive elimination reaction. The hoop-shaped molecules can be directly viewed by a STM technique. In addition, chiral enantiomers with (-)/(+) helicity of the [4]CAn_2,6 were successfully isolated by HPLC. The new tubular CNT segments exhibit large absorption and photoluminescence redshifts compared to the monomer unit. The carbon enantiomers are also observed to show strong circularly polarized luminescence (g_lum ≈0.1). The results reported here expand the scope of materials design for bottom-up synthesis of chiral macrocycles and enrich existing knowledge of their optoelectronic properties.

Keywords: chirality; conjugation; macrocycles; nanotubes; photophysics.

Abstract

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