Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework

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Cliffe, MJ 
Castillo-Martínez, E 
Forse, AC 

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.

0302 Inorganic Chemistry
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Journal of the American Chemical Society
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American Chemical Society
Engineering and Physical Sciences Research Council (EP/N001583/1)
European Commission (659764)
M.J.C. was supported by Sidney Sussex College, Cambridge; M.J.C., J.A.H., and A.L.G. were supported by the European Research Council (279705); and J.L., A.C.F., E.C.-M., and C.P.G. were supported by the Engineering and Physical Sciences Research Council (U.K.) under the Supergen Consortium and Grant (EP/N001583/1). D.F.-J. thanks the Royal Society for funding through a University Research Fellowship. The Diamond Light Source Ltd. (beamlines I11 (EE9940, EE15118), I12 (EE12554), and I15 (EE13681, EE13843) is thanked for providing beamtime. Via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service ( Part of this work was performed using the Darwin Supercomputer of the University of Cambridge High Performance Computing Service (, provided by Dell Inc. using Strategic Research Infrastructure Funding from the Higher Education Funding Council for England and funding from the Science and Technology Facilities Council.