title: Regioselective Atomic Layer Deposition in Metal-Organic Frameworks Directed by Dispersion Interactions.
abstract: The application of atomic layer deposition (ALD) to metal-organic frameworks (MOFs) offers a promising new approach to synthesize designer functional materials with atomic precision. While ALD on flat substrates is well established, the complexity of the pore architecture and surface chemistry in MOFs present new challenges. Through in situ synchrotron X-ray powder diffraction, we visualize how the deposited atoms are localized and redistribute within the MOF during ALD. We demonstrate that the ALD is regioselective, with preferential deposition of oxy-Zn(II) species within the small pores of NU-1000. Complementary density functional calculations indicate that this startling regioselectivity is driven by dispersion interactions associated with the preferential adsorption sites for the organometallic precursors prior to reaction.
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439-4858, United States.
authors.forename: Leighanne C
authors.initials: LC
authors.lastname: Gallington
authors.affiliation: Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: In Soo
authors.initials: IS
authors.lastname: Kim
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455-0431, United States.
authors.forename: Wei-Guang
authors.initials: WG
authors.lastname: Liu
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439-4858, United States.
authors.forename: Andrey A
authors.initials: AA
authors.lastname: Yakovenko
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439-4858, United States.
authors.forename: Ana E
authors.initials: AE
authors.lastname: Platero-Prats
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Zhanyong
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Wang
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.
authors.forename: Joseph T
authors.initials: JT
authors.lastname: Hupp
authors.affiliation: Department of Chemistry, Northwestern University , Evanston, Illinois 60208-3113, United States.|Department of Chemistry, Faculty of Science, King Abdulaziz University , Jeddah 21589, Saudi Arabia.
authors.forename: Omar K
authors.initials: OK
authors.lastname: Farha
authors.affiliation: Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota , Minneapolis, Minnesota 55455-0431, United States.
authors.forename: Donald G
authors.initials: DG
authors.lastname: Truhlar
authors.affiliation: Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
authors.forename: Alex B F
authors.initials: ABF
authors.lastname: Martinson
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , Argonne, Illinois 60439-4858, United States.
authors.forename: Karena W
authors.initials: KW
authors.lastname: Chapman