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Leveraging Ligand Steric Demand to Control Linker Exchange and Fine-Tune Domain Building Block Composition in Stratified Metal-Organic Frameworks

De Souza, Mattheus (2021) Leveraging Ligand Steric Demand to Control Linker Exchange and Fine-Tune Domain Building Block Composition in Stratified Metal-Organic Frameworks. Master's Thesis, University of Pittsburgh. (Unpublished)

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Incorporation of a variety of components into structural and functional domains within metal-organic frameworks (MOFs) has been shown to reveal new properties that expand the scope of potential applications. Stratified MOFs (sMOFs) are a class of multicomponent MOFs consisting of two or more compositionally unique concentric domains (strata). sMOFs can be encoded with unparalleled complexity through the partitioning of structural components into domain building blocks (DBBs). However, the labile nature of metal-linker coordination in MOFs handicaps achieving pristine DBBs with varied linkers due to linker exchange reactions that occur simultaneously with secondary strata growth. Therefore, to achieve more complex sMOF compositions, it is vital to characterize and control the competing processes of both new strata growth and linker exchange. This work presents a systematic study of how linker exchange can be controlled and mitigated in UiO-67 sMOFs by tuning the steric demand of linkers and length of secondary growth reactions. Post-synthetic soaking of sMOFs in various solvent environments resulted in outcomes ranging from homogeneous mixing in 2 hours to maintained compositional integrity after 13 months. We also report a new approach to sMOF synthesis that allows for mitigation of linker exchange between two non-sterically hindered linkers. We present and employ a quantitative method for assessing and visualizing the outcomes of the competing processes of strata growth and ligand exchange that relies on elemental mapping via scanning transmission electron microscopy energy-dispersive X-ray spectroscopy.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
De Souza, MattheusMLD144@pitt.eduMLD1440000-0002-2057-3610
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairRosi, Nathaniel Lnrosi@pitt.edunrosi0000-0001-8025-8906
Committee MemberMillstone, Jilljem210@pitt.edujem2100000-0002-9499-5744
Committee MemberHernández Sánchez, Raúlraulhs@pitt.eduraulhs
Date: 8 October 2021
Date Type: Publication
Defense Date: 29 April 2021
Approval Date: 8 October 2021
Submission Date: 1 July 2021
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 74
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: MS - Master of Science
Thesis Type: Master's Thesis
Refereed: Yes
Uncontrolled Keywords: Metal-organic framework Linker exchange
Date Deposited: 08 Oct 2021 18:48
Last Modified: 08 Oct 2021 18:48


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