Metal–organic nanosheets formed via defect-mediated transformation of a hafnium metal–organic framework

Cliffe, Matthew J.; Castillo-Mart�nez, Elizabeth; Wu, Yue; Lee, Jeongjae; Forse, Alexander C.; Firth, Francesca C. N.; Moghadam, Peyman Z.; Fairen-Jimenez, David; Gaultois, Michael W.; Hill, Joshua A.; Magdysyuk, Oxana V.; Slater, Ben; Goodwin, Andrew L.; Grey, Clare P.

Abstract

We report a hafnium-containing MOF, hcp UiO-67(Hf), which is a ligand-deficient layered analogue of the face-centered cubic fcu UiO-67(Hf). hcp UiO-67 accommodates its lower ligand:metal ratio compared to fcu UiO-67 through a new structural mechanism: the formation of a condensed “double cluster” (Hf12O8(OH)14), analogous to the condensation of coordination polyhedra in oxide frameworks. In oxide frameworks, variable stoichiometry can lead to more complex defect structures, e.g., crystallographic shear planes or modules with differing compositions, which can be the source of further chemical reactivity; likewise, the layered hcp UiO-67 can react further to reversibly form a two-dimensional metal–organic framework, hxl UiO-67. Both three-dimensional hcp UiO-67 and two-dimensional hxl UiO-67 can be delaminated to form metal–organic nanosheets. Delamination of hcp UiO-67 occurs through the cleavage of strong hafnium-carboxylate bonds and is effected under mild conditions, suggesting that defect-ordered MOFs could be a productive route to porous two-dimensional materials.

Citation

Cliffe, M. J., Castillo-Martínez, E., Wu, Y., Lee, J., Forse, A. C., Firth, F. C. N., …Grey, C. P. (2017). Metal–organic nanosheets formed via defect-mediated transformation of a hafnium metal–organic framework. Journal of the American Chemical Society, 139(15), 5397-5404. https://doi.org/10.1021/jacs.7b00106

• Journal Article Type: Article
• Acceptance Date: Mar 25, 2017
• Online Publication Date: Mar 27, 2017
• Publication Date: Apr 19, 2017
• Deposit Date: Dec 20, 2018
• Publicly Available Date: Dec 20, 2018
• Journal: Journal of the American Chemical Society
• Print ISSN: 0002-7863
• Electronic ISSN: 1520-5126
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 139
• Issue: 15
• Pages: 5397-5404
• DOI: https://doi.org/10.1021/jacs.7b00106
• Public URL: https://nottingham-repository.worktribe.com/output/1430950
• Publisher URL: https://pubs.acs.org/doi/10.1021/jacs.7b00106
• Contract Date: Dec 20, 2018