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



Yue Wu

Jeongjae Lee

Alexander C. Forse

Francesca C. N. Firth

Peyman Z. Moghadam

David Fairen-Jimenez

Michael W. Gaultois

Joshua A. Hill

Oxana V. Magdysyuk

Ben Slater

Andrew L. Goodwin

Clare P. Grey


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.


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.

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
Public URL
Publisher URL


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