Metal-Organic Nanosheets Formed via Defect-Mediated Transformation of a Hafnium Metal-Organic Framework.
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.
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Matthew J
0000-0002-0408-7647
MJ
Cliffe
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Elizabeth
0000-0002-8577-9572
E
Castillo-Martínez
Department of Materials Science & Metallurgy, University of Cambridge , 27 Charles Babbage Road, Cambridge CB3 0FS, U.K.
Yue
0000-0003-2874-8267
Y
Wu
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Jeongjae
J
Lee
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Alexander C
AC
Forse
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Francesca C N
FCN
Firth
Department of Chemical Engineering and Biotechnology, University of Cambridge , Pembroke Street, Cambridge CB2 3RA, U.K.
Peyman Z
0000-0002-1592-0139
PZ
Moghadam
Department of Chemical Engineering and Biotechnology, University of Cambridge , Pembroke Street, Cambridge CB2 3RA, U.K.
David
D
Fairen-Jimenez
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Michael W
MW
Gaultois
Department of Chemistry, University of Oxford , South Parks Road, Oxford OX1 3QR, U.K.
Joshua A
JA
Hill
Diamond Light Source Ltd. , Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, U.K.
Oxana V
OV
Magdysyuk
Department of Chemistry, University College London , 20 Gordon Street, London WC1H 0AJ, U.K.
Ben
B
Slater
Department of Chemistry, University of Oxford , South Parks Road, Oxford OX1 3QR, U.K.
Andrew L
AL
Goodwin
Department of Chemistry, University of Cambridge , Lensfield Road, Cambridge CB2 1EW, U.K.
Clare P
CP
Grey