Controlling the photochromism of zirconium pyromellitic diimide-based metal-organic frameworks through coordinating solvents

Metal-organic frameworks (MOFs) are promising platforms for designing photoresponsive materials due to their structural versatility and tunable properties. However, challenges remain in fine-tuning the photoresponsive behavior while maintaining the high stability of MOFs. In this study, we synthesiz...

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Bibliographic Details
Published in:Molecular systems design & engineering 2024-11, Vol.9 (12), p.1228-1234
Main Authors: Li, Youcong, Dong, Jiahao, Zhao, Yue, Gao, Lei, Gu, Yu-Hao, Yuan, Shuai
Format: Article
Language:English
Subjects:
Bleaching
Clusters
Coordination
Density functional theory
Diimide
Dimethyl sulfoxide
Dimethylformamide
Electron paramagnetic resonance
Electron transfer
Ethanol
Metal-organic frameworks
Photochromism
Single crystals
Solvents
Zirconium
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Summary:Metal-organic frameworks (MOFs) are promising platforms for designing photoresponsive materials due to their structural versatility and tunable properties. However, challenges remain in fine-tuning the photoresponsive behavior while maintaining the high stability of MOFs. In this study, we synthesized a MOF containing redox-active pyromellitic diimide (PMDI) groups and unsaturated Zr 6 clusters named Zr-PMDI-DMF and fine-tuned its photochromic properties by exchanging the coordination solvent molecules on the Zr sites. Unlike traditional Zr 6 clusters with bidentate carboxylate coordination, Zr-PMDI-DMF features monodentate carboxylate coordination with the exposed Zr sites occupied by solvent molecules. We post-synthetically exchanged the coordinated N , N -dimethylformamide (DMF) solvent molecules with 2-(dimethylamino)ethanol (DMAE), N -methyltetrahydropyrrole (NMP), and dimethyl sulfoxide (DMSO) and determined the structures of the coordinated solvent molecules using single-crystal X-ray diffraction. Through photochromic and bleaching cycle experiments, electron paramagnetic resonance spectroscopy, and density functional theory calculations, we found that the coordinated solvents act as electron donors. In contrast, PMDI ligands act as electron acceptors, causing intra-framework electron transfer and photochromism. The rate of the photochromic response correlated with the electron-donating ability of the solvents, following the trend of DMAE > NMP > DMSO > DMF. Coordinating solvent-controlled photochromism.
ISSN:2058-9689
2058-9689
DOI:10.1039/d4me00104d