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Scorpionate‐Type Coordination in MFU‐4 l Metal–Organic Frameworks: Small‐Molecule Binding and Activation upon the Thermally Activated Formation of Open Metal Sites
Abstract
Postsynthetic metal and ligand exchange is a versatile approach towards functionalized MFU‐4 l frameworks. Upon thermal treatment of MFU‐4 l formates, coordinatively strongly unsaturated metal centers, such as zinc(II) hydride or copper(I) species, are generated selectively. Cu I‐MFU‐4 l prepared in this way was stable under ambient conditions and showed fully reversible chemisorption of small molecules, such as O 2, N 2, and H 2, with corresponding isosteric heats of adsorption of 53, 42, and 32 kJ mol−1, respectively, as determined by gas‐sorption measurements and confirmed by DFT calculations. Moreover, Cu I‐MFU‐4 l formed stable complexes with C 2 H 4 and CO. These complexes were characterized by FTIR spectroscopy. The demonstrated hydride transfer to electrophiles and strong binding of small gas molecules suggests these novel, yet robust, metal–organic frameworks with open metal sites as promising catalytic materials comprising earth‐abundant metal elements.
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Metal hydride materials for solid hydrogen storage: A review
SAKINTUNA, B., LAMARIDARKRIM, F., & HIRSCHER, M. (2007) · International Journal of Hydrogen Energy · doi:10.1016/j.ijhydene.2006.11.022 · Cited by 3,715
Cited by
Hadjiivanov, K. I., Panayotov, D. A., Mihaylov, M. Y., Ivanova, E. Z., Chakarova, K. K., Andonova, S. M., & Drenchev, N. L. (2021) · Chemical Reviews · doi:10.1021/acs.chemrev.0c00487 · Cited by 1,278
Kökçam-Demir, Ü., Goldman, A., Esrafili, L., Gharib, M., Morsali, A., Weingart, O., & Janiak, C. (2020) · Chemical Society Reviews · doi:10.1039/c9cs00609e · Cited by 895
Porous materials for hydrogen storage
Chen, Z., Kirlikovali, K. O., Idrees, K. B., Wasson, M. C., & Farha, O. K. (2022) · Chem · doi:10.1016/j.chempr.2022.01.012 · Cited by 543
Grand Challenges and Future Opportunities for Metal–Organic Frameworks
Hendon, C. H., Rieth, A. J., Korzyński, M. D., & Dincă, M. (2017) · ACS Central Science · doi:10.1021/acscentsci.7b00197 · Cited by 434
Kinetic stability of metal–organic frameworks for corrosive and coordinating gas capture
Rieth, A. J., Wright, A. M., & Dincă, M. (2019) · Nature Reviews Materials · doi:10.1038/s41578-019-0140-1 · Cited by 402
Metadata
- Authors
- Denysenko, D., Grzywa, M., Jelic, J., Reuter, K., & Volkmer, D.
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2014-05-20
- Volume
- 53
- Issue
- 23
- Pages
- 5832-5836
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2114627871
- Cited by
- 175
- References
- 1
- FWCI
- 4.66
- Type
- journal article
- Language
- en
- Open access
- closed
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- Denysenko, D., Grzywa, M., Jelic, J., Reuter, K., & Volkmer, D. (2014). Scorpionate‐Type Coordination in MFU‐4 l Metal–Organic Frameworks: Small‐Molecule Binding and Activation upon the Thermally Activated Formation of Open Metal Sites. Angewandte Chemie International Edition. https://doi.org/10.1002/anie.201310004
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