Surface-Specific Functionalization of Nanoscale Metal-Organic Frameworks

Shunzhi Wang; William Morris; Yangyang Liu; C Michael McGuirk; Yu Zhou; Joseph T Hupp; Omar K Farha; Chad A Mirkin

doi:10.1002/anie.201506888

Surface-Specific Functionalization of Nanoscale Metal-Organic Frameworks

Angew Chem Int Ed Engl. 2015 Dec 1;54(49):14738-42. doi: 10.1002/anie.201506888. Epub 2015 Oct 23.

Authors

Shunzhi Wang¹, William Morris², Yangyang Liu¹, C Michael McGuirk¹, Yu Zhou³, Joseph T Hupp¹, Omar K Farha^{1

4}, Chad A Mirkin^{5

6

7}

Affiliations

¹ Department of Chemistry, Northwestern University, Evanston, IL (USA).
² International Institute for Nanotechnology, Northwestern University, Evanston, IL (USA).
³ Department of Material Science and Engineering, Northwestern University, Evanston, IL (USA).
⁴ Department of Chemistry, King Abdulaziz University, Jeddah (Saudi Arabia).
⁵ Department of Chemistry, Northwestern University, Evanston, IL (USA). chadnano@northwestern.edu.
⁶ International Institute for Nanotechnology, Northwestern University, Evanston, IL (USA). chadnano@northwestern.edu.
⁷ Department of Material Science and Engineering, Northwestern University, Evanston, IL (USA). chadnano@northwestern.edu.

PMID: 26492949
DOI: 10.1002/anie.201506888

Abstract

A method for modifying the external surfaces of a series of nanoscale metal-organic frameworks (MOFs) with 1,2-dioleoyl-sn-glycero-3-phosphate (DOPA) is presented. A series of zirconium-based nanoMOFs of the same topology (UiO-66, UiO-67, and BUT-30) were synthesized, isolated as aggregates, and then conjugated with DOPA to create stably dispersed colloids. BET surface area analysis revealed that these structures maintain their porosity after surface functionalization, providing evidence that DOPA functionalization only occurs on the external surface. Additionally, dye-labeled ligand loading studies revealed that the density of DOPA on the surface of the nanoscale MOF correlates to the density of metal nodes on the surface of each MOF. Importantly, the surface modification strategy described will allow for the general and divergent synthesis and study of a wide variety of nanoscale MOFs as stable colloidal materials.

Keywords: metal-organic frameworks; phosphate lipids; post-synthetic modification; surface functionalization; zirconium oxo clusters.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.