Noncovalent Surface Modification of Metal-Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

Thomas R. Sheridan; Madeleine A. Gaidimas; Boris V. Kramar; Subhadip Goswami; Lin X. Chen; Omar K. Farha; Joseph T. Hupp

doi:10.1021/acs.langmuir.2c01223

Noncovalent Surface Modification of Metal-Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

Thomas R. Sheridan, Madeleine A. Gaidimas, Boris V. Kramar, Subhadip Goswami, Lin X. Chen, Omar K. Farha, Joseph T. Hupp^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

Despite the importance of noncovalent interactions in the utilization of metal-organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy)₂(bpy-R)]²⁺-functionalized dyes with the surface of MIL-96, where R = C₃, C₈, C₁₂, and C₁₈alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.

Original language	English (US)
Pages (from-to)	11199-11209
Number of pages	11
Journal	Langmuir
Volume	38
Issue number	37
DOIs	https://doi.org/10.1021/acs.langmuir.2c01223
State	Published - Sep 20 2022

Funding

J.T.H. gratefully acknowledges support from the U.S. Department of Energy, Office of Science, Basic Energy Sciences (Grant DE-FG02-87ER13808). O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-18-1-0003). This work was also supported by the National Defense Science and Engineering Program Graduate Fellowship (NDSEG). For the work performed at Northwestern, this work made use of the Integrated Molecular Structure Education and Research Center (IMSERC) facility at Northwestern University, which has received support from the National Science Foundation (NSF, CHE-1048773 and DMR-0521267), the Electron Probe Instrumentation Center (EPIC) and the Keck Interdisciplinary Surface Science (Keck-II) facilities of the Northwestern University Atomic and Nanoscale Characterization Experimental (NUANCE) Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern’s Materials Research Science and Engineering Center (MRSEC) program (NSF, DMR-1720139).

ASJC Scopus subject areas

Condensed Matter Physics
Spectroscopy
General Materials Science
Surfaces and Interfaces
Electrochemistry

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title = "Noncovalent Surface Modification of Metal-Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry",

abstract = "Despite the importance of noncovalent interactions in the utilization of metal-organic frameworks (MOFs), using these interactions to functionalize MOFs has rarely been explored. The ease of functionalization and potential for surface-selective functionalization makes modification via noncovalent interactions promising for the creation of porous photocatalytic assemblies. Using isothermal titration calorimetry, photoluminescence measurements, and desorption experiments, we have explored the nature and magnitude of the interactions of [Ru(bpy)2(bpy-R)]2+-functionalized dyes with the surface of MIL-96, where R = C3, C8, C12, and C18alkyl chains of either straight-chain or cyclic conformations. The orientation of the dyes appears to be flat against the surface with respect to the long alkyl chains, and the surface concentration approaches a monolayer at high initial concentrations of dye. Strangely, the dodecyl-functionalized dye, despite having a smaller interaction energy and larger footprint than either octyl-functionalized dye, achieves the highest maximum surface concentration. Based on photoluminescence spectra, desorption experiments, and ITC data, we believe this is due to the core of the dye being lifted from the surface as the chain length increases. Our understanding of these interactions is important for further utilization of this method for the functionalization of the internal and external surface areas of MOFs.",

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Noncovalent Surface Modification of Metal-Organic Frameworks: Unscrambling Adsorption Properties via Isothermal Titration Calorimetry

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