Solvent-free construction of Cr(iii)-sulfonate coordination polymers

Abstract

Constructing sulfonate coordination polymers (CPs) with high stability remains a significant challenge due to the relatively weak coordination ability of the sulfonate group, especially when paired with highly inert Cr3+ ions. In this study, we designed solvent-free methods to enhance Cr(III)-sulfonate coordination and further advance its reticular chemistry. For the first time, two Cr(III)-sulfonate CPs, TGU-9 and TGU-10, were successfully constructed, along with two supramolecules, TGU-7 and TGU-8. All structures were elucidated using the 3D electron diffraction technique. Through solvent-free methods, Cr(III)-sulfonate coordination was achieved by a double displacement reaction between Cr salts and –SO3H groups. In particular, this method resulted in a counterintuitive coordination reversal from –COO > –SO3 to –SO3 > –COO. Reaction mechanism analysis revealed that the higher acidity of the –SO3H group, compared to the –COOH group, leads to its preferential deprotonation, thereby facilitating the kinetics of Cr-sulfonate self-assembly. Furthermore, both TGU-9 and TGU-10 exhibited exceptional long-term stability under ambient conditions and over a wide pH range. They also showed high proton conductivity exceeding 10−2 S cm−1, ranking in the top two among the reported sulfonate CPs. The designed solvent-free method demonstrated a generally applicable and simple strategy in designing novel metal–ligand coordination and constructing reticular chemistry, beyond the limitations of conventional solvent-based methods.

Graphical abstract: Solvent-free construction of Cr(iii)-sulfonate coordination polymers

Supplementary files

Article information

Article type
Edge Article
Submitted
24 Apr 2025
Accepted
30 May 2025
First published
31 May 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2025, Advance Article

Solvent-free construction of Cr(III)-sulfonate coordination polymers

F. Yang, X. Kong, T. He, Z. Zhang, K. Wang, H. Du, G. Cai, J. Ju, X. Wang, J. Li, J. Sun and C. Zhong, Chem. Sci., 2025, Advance Article , DOI: 10.1039/D5SC03014E

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