Metal-hydrogen-pi-bonded organic frameworks
Abstract
We report the synthesis and characterization of a new series of permanently porous, three-dimensional metal–organic frameworks (MOFs), M-HAF-2 (M = Fe, Ga, or In), constructed from tetratopic, hydroxamate-based, chelating linkers. Here, the structure of M-HAF-2 was determined by three-dimensional electron diffraction (3D ED), revealing a unique interpenetrated hcb-a net topology. This unusual topology is enabled by the presence of free hydroxamic acid groups, which lead to the formation of a diverse network of cooperative interactions comprising metal–hydroxamate coordination interactions at single metal nodes, staggered π–π interactions between linkers, and H-bonding interactions between metal-coordinated and free hydroxamate groups. Such extensive, multimodal interconnectivity is reminiscent of the complex, noncovalent interaction networks of proteins and endows M-HAF-2 frameworks with high thermal and chemical stability and allows them to readily undergo postsynthetic metal ion exchange (PSE) between trivalent metal ions. We demonstrate that M-HAF-2 can serve as versatile porous materials for ionic separations, aided by one-dimensional channels lined by continuously π-stacked aromatic groups and H-bonding hydroxamate functionalities. As an addition to the small group of hydroxamic acid-based MOFs, M-HAF-2 represents a structural merger between MOFs and hydrogen-bonded organic frameworks (HOFs) and illustrates the utility of non-canonical metal-coordinating functionalities in the discovery of new bondingmore »
- Authors:
-
- Univ. of California, San Diego, La Jolla, CA (United States)
- Stockholm Univ. (Sweden)
- Publication Date:
- Research Org.:
- Univ. of California, San Diego, La Jolla, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Swedish Research Council Formas; Knut and Alice Wallenberg Foundation; USDOE
- OSTI Identifier:
- 1871937
- Alternate Identifier(s):
- OSTI ID: 1839476; OSTI ID: 1922337
- Grant/Contract Number:
- FG02-08ER46519; SC0003844
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 5; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MOFs; hydroxamic acids; hydroxamate-based
Citation Formats
Zhu, Jie, Samperisi, Laura, Kalaj, Mark, Chiong, Jerika A., Bailey, Jake B., Zhang, Zhiyin, Yu, Chung-Jui, Sikma, R. Eric, Zou, Xiaodong, Cohen, Seth M., Huang, Zhehao, and Tezcan, F. Akif. Metal-hydrogen-pi-bonded organic frameworks. United States: N. p., 2022.
Web. doi:10.1039/d1dt04278e.
Zhu, Jie, Samperisi, Laura, Kalaj, Mark, Chiong, Jerika A., Bailey, Jake B., Zhang, Zhiyin, Yu, Chung-Jui, Sikma, R. Eric, Zou, Xiaodong, Cohen, Seth M., Huang, Zhehao, & Tezcan, F. Akif. Metal-hydrogen-pi-bonded organic frameworks. United States. https://doi.org/10.1039/d1dt04278e
Zhu, Jie, Samperisi, Laura, Kalaj, Mark, Chiong, Jerika A., Bailey, Jake B., Zhang, Zhiyin, Yu, Chung-Jui, Sikma, R. Eric, Zou, Xiaodong, Cohen, Seth M., Huang, Zhehao, and Tezcan, F. Akif. Wed .
"Metal-hydrogen-pi-bonded organic frameworks". United States. https://doi.org/10.1039/d1dt04278e. https://www.osti.gov/servlets/purl/1871937.
@article{osti_1871937,
title = {Metal-hydrogen-pi-bonded organic frameworks},
author = {Zhu, Jie and Samperisi, Laura and Kalaj, Mark and Chiong, Jerika A. and Bailey, Jake B. and Zhang, Zhiyin and Yu, Chung-Jui and Sikma, R. Eric and Zou, Xiaodong and Cohen, Seth M. and Huang, Zhehao and Tezcan, F. Akif},
abstractNote = {We report the synthesis and characterization of a new series of permanently porous, three-dimensional metal–organic frameworks (MOFs), M-HAF-2 (M = Fe, Ga, or In), constructed from tetratopic, hydroxamate-based, chelating linkers. Here, the structure of M-HAF-2 was determined by three-dimensional electron diffraction (3D ED), revealing a unique interpenetrated hcb-a net topology. This unusual topology is enabled by the presence of free hydroxamic acid groups, which lead to the formation of a diverse network of cooperative interactions comprising metal–hydroxamate coordination interactions at single metal nodes, staggered π–π interactions between linkers, and H-bonding interactions between metal-coordinated and free hydroxamate groups. Such extensive, multimodal interconnectivity is reminiscent of the complex, noncovalent interaction networks of proteins and endows M-HAF-2 frameworks with high thermal and chemical stability and allows them to readily undergo postsynthetic metal ion exchange (PSE) between trivalent metal ions. We demonstrate that M-HAF-2 can serve as versatile porous materials for ionic separations, aided by one-dimensional channels lined by continuously π-stacked aromatic groups and H-bonding hydroxamate functionalities. As an addition to the small group of hydroxamic acid-based MOFs, M-HAF-2 represents a structural merger between MOFs and hydrogen-bonded organic frameworks (HOFs) and illustrates the utility of non-canonical metal-coordinating functionalities in the discovery of new bonding and topological patterns in reticular materials.},
doi = {10.1039/d1dt04278e},
journal = {Dalton Transactions},
number = 5,
volume = 51,
place = {United States},
year = {Wed Jan 05 00:00:00 EST 2022},
month = {Wed Jan 05 00:00:00 EST 2022}
}
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