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Peer-reviewedCC BY-NC-ND 4.0JACS Au

meta -Carborane-Based Macrocyclic Arenes: Synthesis and Inner-Wall Modification

  • Ying-Zheng Ren1,2
  • Xiao-Jian Ren3
  • Lu-Qi Guo1
  • Lin-Yan Xia1
  • Xin-Ran Liu4
  • Peng-Fei Cui1,5,6
6 affiliations
  1. 1Nanjing University of Science and Technology , , ,
  2. 2Heze University , , ,
  3. 3Hebei Agricultural University , , ,
  4. 4Nanjing University , , ,
  5. 5Shanxi Applied Physics and Chemistry Research Institute , , ,
  6. 6The Key Laboratory of Functional Molecular Solids, Ministry of Education , ,
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Abstract

Precise inner-wall modification of macrocyclic arenes remains a formidable challenge in supramolecular chemistry due to the scarcity of available synthetic strategies. Herein, we report the design and synthesis of a novel meta-carborane-based macrocyclic arene featuring a rigid triangular prismatic cavity. By finely tuning the stoichiometry of tetrabutylammonium fluoride (TBAF), we achieved the first stepwise inner-wall functionalization of this macrocyclic system via the controllable deboronation of closo-meta-carborane units, selectively affording mono-, bis-, and tris-nido-carborane-modified products in high isolated yields. This approach enables programmable modulation of the cavity electrostatic microenvironment under mild conditions with high site selectivity. In addition, a metal-free oxidative B–N coupling reaction was employed to achieve inner-wall postmodification. Notably, covalent attachment of fluorophores to the macrocyclic scaffold leads to a significant enhancement of emission intensity, which is tentatively attributed to the restriction of intramolecular motions (RIM) imposed by the macrocyclic framework. This work establishes a new paradigm for the inner-wall engineering of macrocyclic arenes and substantially broadens the application horizons of carborane-based supramolecular chemistry.

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Cite

BibTeXRIS
BibTeX
@article{ren2026meta,
  title = {{meta -Carborane-Based Macrocyclic Arenes: Synthesis and Inner-Wall Modification}},
  author = {Ying-Zheng Ren and Xiao-Jian Ren and Lu-Qi Guo and Lin-Yan Xia and Xin-Ran Liu and Peng-Fei Cui},
  journal = {JACS Au},
  year = {2026},
  month = oct,
  doi = {10.1021/jacsau.6c01203},
  url = {https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01203/5454107/meta-Carborane-Based-Macrocyclic-Arenes-Synthesis},
  note = {CC BY-NC-ND 4.0},
}
RIS
TY  - JOUR
TI  - meta -Carborane-Based Macrocyclic Arenes: Synthesis and Inner-Wall Modification
AU  - Ying-Zheng Ren
AU  - Xiao-Jian Ren
AU  - Lu-Qi Guo
AU  - Lin-Yan Xia
AU  - Xin-Ran Liu
AU  - Peng-Fei Cui
PY  - 2026
DA  - 2026/10/20
JO  - JACS Au
DO  - 10.1021/jacsau.6c01203
UR  - https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c01203/5454107/meta-Carborane-Based-Macrocyclic-Arenes-Synthesis
AB  - Precise inner-wall modification of macrocyclic arenes remains a formidable challenge in supramolecular chemistry due to the scarcity of available synthetic strategies. Herein, we report the design and synthesis of a novel meta-carborane-based macrocyclic arene featuring a rigid triangular prismatic cavity. By finely tuning the stoichiometry of tetrabutylammonium fluoride (TBAF), we achieved the first stepwise inner-wall functionalization of this macrocyclic system via the controllable deboronation of closo-meta-carborane units, selectively affording mono-, bis-, and tris-nido-carborane-modified products in high isolated yields. This approach enables programmable modulation of the cavity electrostatic microenvironment under mild conditions with high site selectivity. In addition, a metal-free oxidative B–N coupling reaction was employed to achieve inner-wall postmodification. Notably, covalent attachment of fluorophores to the macrocyclic scaffold leads to a significant enhancement of emission intensity, which is tentatively attributed to the restriction of intramolecular motions (RIM) imposed by the macrocyclic framework. This work establishes a new paradigm for the inner-wall engineering of macrocyclic arenes and substantially broadens the application horizons of carborane-based supramolecular chemistry.
SN  - 2691-3704
ER  -