Citation: Pengfei Niu, Jiawei Ma, Beijing Zhang, Ziyao Nie, Haitao Liu, Yong Liang, Xing Jiang. Shape-persistent hexa(ethynylpyridine) macrocycles as adaptive hosts for cations[J]. Chinese Chemical Letters, ;2026, 37(8): 112429. doi: 10.1016/j.cclet.2026.112429 shu

Shape-persistent hexa(ethynylpyridine) macrocycles as adaptive hosts for cations

Pengfei Niu ^{a, b} ,
Jiawei Ma ^c ,
Beijing Zhang ^{a, b} ,
Ziyao Nie ^{a, b} ,
Haitao Liu ^{a, b} ,
Yong Liang ^c ,
Xing Jiang ^{a, b, *,}

a.
South China Advanced Institute for Soft Matter Science and Technology School of Emergent Soft Matter, South China University of Technology, Guangzhou 510640, China
b.
Guangdong Provincial Key Laboratory of Functional and Intelligent Hybrid Materials and Devices, South China University of Technology, Guangzhou 510640, China
c.
School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

xingj@scut.edu.cn

Received Date: 1 August 2025
Revised Date: 14 January 2026
Accepted Date: 18 January 2026
Available Online: 14 April 2026

Figures(6)

We present the synthesis and host-guest complexation of endo-functionalized shape-persistent hexa(ethynylpyridine) macrocycles (Py₆MCs). The challenging macrocyclization of linear hexapyridine precursors was achieved by using catalytic amount of PdCl₂(PPh₃)₂ and stoichiometric CuI in the Sonogashira reaction, or with K₂CO₃ as an additive under copper-free conditions. Single-crystal X-ray diffraction revealed that Py₆MCs with different side chains all feature a near-planar framework, with notable flexibility to adopt chair-like or boat-like conformations. The polar and electron-rich cavities of Py₆MCs render them attractive hosts for cationic guests. ¹H NMR and fluorescence titrations showed that Py₆MC1 and Py₆MC2 formed 1:1 complexes with N-methyl pyridinium and quaternary ammonium cations, and high affinity (up to 3.1 × 10⁵ L/mol) was achieved for cations of distinct shapes and sizes. Density functional theory (DFT) calculations showed that Py₆MC readily deforms to complement the structures of different guests, demonstrating a high level of adaptivity.
- Shape-persistent macrocycles,
- Endo-functionalization,
- Adaptive,
- Host–guest chemistry,
- Sonogashira reaction
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