Supramolecular Halogen-Bonded Organic Frameworks (XOFs): From Structural Construction to Functional Applications
- 1Wuhan University , , , ,
Abstract
Supramolecular halogen-bonded organic frameworks (XOFs) have emerged as a distinct class of crystalline material in which halogen bonding, rather than covalent or coordination chemistry, defines the framework. Two types of XOFs have developed. Classical XOFs are assembled from electroneutral R–X···D contacts; their single-point character biases assembly toward chains, sheets, and three-dimensional networks. Cationic XOFs exploit halonium ions, whose vacant p orbital bridges two Lewis bases in a three-center, four-electron [N···X···N]+ motif. The halogen scope has widened from iodine(I) through bromine(I) to chlorine(I), a species otherwise observable only transiently at cryogenic temperatures. This review surveys both families with respect to structural classification, synthetic strategy─from cocrystallization to silver–halogen exchange, and dynamic ligand exchange─and functional application, including gas adsorption and separation, iodine capture, photocatalysis, luminescent and vapochromic sensing, and biomedicine. Halogen bonding offers an assembly logic tunable through halogen identity, counterion, and ligand that has no direct analogue in coordination or covalent chemistry.
Related
- Acetylation of quinoa starch: structural and functional improvements for food and industrial applications
- Precise construction of antiparallel-stacked 2D imine covalent organic frameworks for atmospheric water harvesting
- Structural, supramolecular and computational insights into the ALS inhibitor pyroxsulam: crystal structure, reactivity and bioactivity
- Fluorescent Metal–Organic Frameworks for Chemical Sensing: Design Strategies, Mechanisms, and Analytical Applications
- Thermodynamic and Structural Evidence for Higher-Order Selegiline with Carboxymethyl-β-Cyclodextrin Supramolecular Assemblies in Aqueous Solution.
BibTeX
@article{zhang2026supramolecular,
title = {{Supramolecular Halogen-Bonded Organic Frameworks (XOFs): From Structural Construction to Functional Applications}},
author = {Meimei Zhang and Qianning He and Xuguan Bai and Lu Wang and Shigui Chen},
journal = {ACS Omega},
year = {2026},
month = oct,
doi = {10.1021/acsomega.6c09016},
url = {https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c09016/5454046/Supramolecular-Halogen-Bonded-Organic-Frameworks},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Supramolecular Halogen-Bonded Organic Frameworks (XOFs): From Structural Construction to Functional Applications
AU - Meimei Zhang
AU - Qianning He
AU - Xuguan Bai
AU - Lu Wang
AU - Shigui Chen
PY - 2026
DA - 2026/10/20
JO - ACS Omega
DO - 10.1021/acsomega.6c09016
UR - https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c09016/5454046/Supramolecular-Halogen-Bonded-Organic-Frameworks
AB - Supramolecular halogen-bonded organic frameworks (XOFs) have emerged as a distinct class of crystalline material in which halogen bonding, rather than covalent or coordination chemistry, defines the framework. Two types of XOFs have developed. Classical XOFs are assembled from electroneutral R–X···D contacts; their single-point character biases assembly toward chains, sheets, and three-dimensional networks. Cationic XOFs exploit halonium ions, whose vacant p orbital bridges two Lewis bases in a three-center, four-electron [N···X···N]+ motif. The halogen scope has widened from iodine(I) through bromine(I) to chlorine(I), a species otherwise observable only transiently at cryogenic temperatures. This review surveys both families with respect to structural classification, synthetic strategy─from cocrystallization to silver–halogen exchange, and dynamic ligand exchange─and functional application, including gas adsorption and separation, iodine capture, photocatalysis, luminescent and vapochromic sensing, and biomedicine. Halogen bonding offers an assembly logic tunable through halogen identity, counterion, and ligand that has no direct analogue in coordination or covalent chemistry.
SN - 2470-1343
ER -