Enhanced Cooperative Lithium Halide Recognition by Heteroditopic Halogen Bonding (XB) Macrocycles
Issued Date
2026-01-12
Resource Type
ISSN
00201669
eISSN
1520510X
Scopus ID
2-s2.0-105027250332
Pubmed ID
41439753
Journal Title
Inorganic Chemistry
Volume
65
Issue
1
Start Page
441
End Page
453
Rights Holder(s)
SCOPUS
Bibliographic Citation
Inorganic Chemistry Vol.65 No.1 (2026) , 441-453
Suggested Citation
Khianjinda T., Vigromsitdet S., Srisawat P., Sawektreeratana N., Tantirungrotechai J., Sukwattanasinitt M., Harding D.J., Beer P.D., Tantirungrotechai Y., Bunchuay T. Enhanced Cooperative Lithium Halide Recognition by Heteroditopic Halogen Bonding (XB) Macrocycles. Inorganic Chemistry Vol.65 No.1 (2026) , 441-453. 453. doi:10.1021/acs.inorgchem.5c04533 Retrieved from: https://repository.li.mahidol.ac.th/handle/123456789/114567
Title
Enhanced Cooperative Lithium Halide Recognition by Heteroditopic Halogen Bonding (XB) Macrocycles
Corresponding Author(s)
Other Contributor(s)
Abstract
A series of macrocyclic heteroditopic receptors was synthesized to investigate cooperative recognition of alkali-metal halide ion pairs. The receptors combine either a 1,3-bis-iodotriazole (XB) or 1,3-bis-prototriazole (HB) benzene scaffold for halide binding with poly(ethylene glycol)-based macrocyclic moieties for cation coordination. Intensive <sup>1</sup>H NMR binding studies revealed that XB-functionalized macrocycles exhibit significantly higher halide affinities than their HB analogues, while increased macrocycle size enhances alkali-metal cation binding strength. Notably, the halide-bound 1·XB macrocycle induced strong positive cooperativity in lithium-ion recognition, with up to a 7-fold increase in binding affinity. Density functional theory (DFT) calculations suggest that electrostatic stabilization between cobound ions underlies this effect, with the most pronounced enhancement observed for the 1·XB@LiI complex. Solid–liquid extraction experiments further demonstrated the practical potential of the XB system, achieving efficient transfer of lithium halide salts into organic solution. These findings establish halogen-bonded macrocycles as effective platforms for cooperative ion-pair recognition and highlight their promise for applications in lithium salt recovery and recycling.