Regioselective ALD in MOFs Directed by Dispersion Interactions

Regioselective Atomic Layer Deposition in Metal–Organic Frameworks Directed by Dispersion Interactions

Leighanne C. Gallington, In Soo Kim, Wei-Guang Liu, Andrey A. Yakovenko, Ana E. Platero-Prats, Zhanyong Li, Timothy C. Wang, Joseph T. Hupp, Omar K. Farha, Donald G. Truhlar, Alex B. F. Martinson, and Karena W. Chapman

J. Am. Chem. Soc., 2016, 138 (41), pp 13513–13516
DOI: 10.1021/jacs.6b08711

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.6b08711.

• Details of X-ray experiments and analysis and computational modeling (PDF)
• Video of evolving difference envelope densities during in situ AIM (AVI)

Picure from graphical abstract showing the MOF process steps in relation to a standard ALD process (used with permission RightsLink(R) Account 3000915597)

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.