Melt-quenched glass formation of a family of metal-carboxylate frameworks

• Published in: Nature communications Vol. 15; no. 1; pp. 2040 - 13
• Main Authors: Xue, Wen-Long, Li, Guo-Qiang, Chen, Hui, Han, Yu-Chen, Feng, Li, Wang, Lu, Gu, Xiao-Ling, Hu, Si-Yuan, Deng, Yu-Heng, Tan, Lei, Dove, Martin T., Li, Wei, Zhang, Jiangwei, Dong, Hongliang, Chen, Zhiqiang, Deng, Wei-Hua, Xu, Gang, Wang, Guo, Wan, Chong-Qing
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 06.03.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 639/301; 639/638; Channels; Glass formation; Grafting; Humanities and Social Sciences; Ligands; Melt temperature; Metal-organic frameworks; Metals; multidisciplinary; Organic acids; Quenching; Science; Science (multidisciplinary); Subsystems; Zeolites; Zwitterions
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-46311-x

Metal-organic framework (MOF) glasses are an emerging class of glasses which complement traditional inorganic, organic and metallic counterparts due to their hybrid nature. Although a few zeolitic imidazolate frameworks have been made into glasses, how to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses remains challenging. Here, we develop a strategy by grafting the zwitterions on the carboxylate ligands and incorporating organic acids in the framework channels to enable the glass formation. The charge delocalization of zwitterion-acid subsystem and the densely filled channels facilitate the coordination bonding mismatch and thus reduce the melting temperature. Following melt-quenching realizes the glass formation of a family of carboxylate MOFs (UiO-67, UiO-68 and DUT-5), which are usually believed to be un-meltable. Our work opens up an avenue for melt-quenching porous molecular solids into glasses. How to melt and quench the largest subclass of MOFs, metal carboxylate frameworks, into glasses is a major challenge. Here, the authors develop a strategy by grafting the zwitterions onto the carboxylate ligands and incorporating organic acids into the framework channels to realize the glass formation.