Citation: Tian Tan, Jiao Hu, Ya-Liang Lai, Xian-Chao Zhou, Yong-Zhen Tan, Mo Xie, Yong-Liang Huang, Chuang-Wei Zhou, Hao-Jie Zhang, Dong Luo, Xiao-Ping Zhou, Dan Li. Enabling guest-binding selectivity in hexahedral metal-organic cages via vertex modification[J]. Chinese Chemical Letters, ;2026, 37(9): 111331. doi: 10.1016/j.cclet.2025.111331 shu

Enabling guest-binding selectivity in hexahedral metal-organic cages via vertex modification

Tian Tan ^a ,
Jiao Hu ^a ,
Ya-Liang Lai ^a ,
Xian-Chao Zhou ^a ,
Yong-Zhen Tan ^a ,
Mo Xie ^a ,
Yong-Liang Huang ^b ,
Chuang-Wei Zhou ^a ,
Hao-Jie Zhang ^a ,
Dong Luo ^{a, *,} ,
Xiao-Ping Zhou ^{a, *,} ,
Dan Li ^a

a.
College of Chemistry and Materials Science, Guangdong Provincial Key Laboratory of Supramolecular Coordination Chemistry, Jinan University, Guangzhou 510632, China
b.
Department of Medicinal Chemistry, Shantou University Medical College, Shantou 515041, China

luodong@jnu.edu.cn

zhouxp@jnu.edu.cn

Received Date: 11 March 2025
Revised Date: 12 May 2025
Accepted Date: 15 May 2025
Available Online: 15 May 2025

Figures(6)

This work investigates the impact of vertex modification on the host-guest chemistry of a hexahedral Zn(Ⅱ)-based metal-organic cage (MOC) 1 containing fluorinated components. Structural characterization via single-crystal X-ray diffraction (SCXRD), ¹H NMR, and electrospray ionization time-of-flight mass spectra (ESI-TOF MS) confirmed the low-symmetry hexahedral architectures of 1·NTf₂ and 1·OTf, with fluorine atoms positioned at cage windows. ¹H/¹⁹F NMR spectra of 1·NTf₂ and 1·OTf showed slow-exchange binding behavior with external anions. 1·NTf₂ had a single set of peaks in the imine signal area, while 1·OTf had two distinct groups of signals. Combined with competitive anion titration results, it can be inferred that NTf₂^- has a stronger binding affinity with the cage structure. Host-guest studies with pyrene (Py) and its hydrogenated analogs revealed complete displacement of OTf^- but not NTf₂^-, highlighting the superior binding strength of NTf₂^-. Comparative isothermal titration calorimetry (ITC) data showed reduced association constants for 1·OTf with pyrene (Py) and its analogs 4,5,9,10-tetrahydropyrene (4H-Py) and hexadecahydropyrene (16H-Py) compared to 2·OTf, attributed to electron-withdrawing fluorine substituents altering charge distribution, which was confirmed by the electrostatic potential analysis of the cage skeleton. These findings underscore how vertex functionalization modulates anion selectivity and guest-binding thermodynamics in MOCs, offering insights for designing tailored supramolecular hosts.
- Metal-organic cage,
- Host-guest chemistry,
- Vertex modification,
- Anion binding,
- Pyrene
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