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oai:dspace.mit.edu:1721.1/1623332025-08-12T03:04:56Zcom_1721.1_7582com_1721.1_7581col_1721.1_131022

Dincă, Mircea Iliescu, Andrei Massachusetts Institute of Technology. Department of Chemistry 2025-08-11T14:19:07Z 2025-08-11T14:19:07Z 2025-05 2025-06-11T15:13:32.815Z https://hdl.handle.net/1721.1/162333 0000-0002-2076-1566 This thesis explores synthetic and post-synthetic strategies for tailoring the chemical and physical properties of metal-organic frameworks (MOFs), with a particular emphasis on modulating redox activity, framework composition, and ionic conductivity. The first part of the work focuses on leveraging MOF-embedded polynuclear metal clusters for multi-electron redox chemistry. A square-planar tetramanganese cluster was shown to reversibly interconvert between molecular oxygen and metal-oxo species via a four-electron pathway. This reactivity was then investigated by varying the identity and redox potential of the metal centers within the tetrametal cluster. The Fe(II) and Co(II) analogs reveal distinct metal-specific behavior and provide insight into the tunability of redox-active SBUs within MOFs. Next, post-synthetic cation exchange was employed to access a previously unreported Zn-based MOF, ZnZnBTT, which exhibits significant Zn-ion conductivity due to mobile charge-balancing cations. This material demonstrates the potential of MOFs in next-generation solid-state battery technologies. Finally, the impact of linker electron donicity on cluster structure and reactivity was explored using a new mixed-azolate ligand. Four isostructural MOFs incorporating Co, Ni, Cu, and Cd were synthesized, revealing that the electron-rich pyrazolate groups modulate cluster composition and redox behavior. Notably, CoBTDP exhibits O₂ reactivity, unlike its all-tetrazolate counterpart, underscoring the role of linker design in tuning MOF function. Together, these studies demonstrate how careful control over MOF synthesis and post-synthetic modification can be used to fine-tune redox behavior, framework composition, and ion transport, providing new avenues for the design of functional porous materials. Ph.D. Massachusetts Institute of Technology Attribution-ShareAlike 4.0 International (CC BY-SA 4.0) Copyright retained by author(s) https://creativecommons.org/licenses/by-sa/4.0/ Synthetic and Post-Synthetic Methods towards Fine Tuning the Chemical and Physical Properties of Metal-Organic Frameworks Thesis application/pdf Doctoral Doctor of Philosophy Publication unknown unknown <Publication xmlns="https://www.openaire.eu/cerif-profile/1.1/" id="5f2c7968-347b-4f08-ac5a-d1dfb3f0a240"> <Type xmlns="https://www.openaire.eu/cerif-profile/vocab/COAR_Publication_Types">http://purl.org/coar/resource_type/c_1843</Type> <Title>Synthetic and Post-Synthetic Methods towards Fine Tuning the Chemical and Physical Properties of Metal-Organic Frameworks</Title> <PublishedIn> <Publication> </Publication> </PublishedIn> <PublicationDate>2025-05</PublicationDate> <Authors> <Author> <DisplayName>Iliescu, Andrei</DisplayName> <Affiliation> <OrgUnit> </OrgUnit> </Affiliation> </Author> </Authors> <Editors> </Editors> <Publishers> <Publisher> <DisplayName>Massachusetts Institute of Technology</DisplayName> <OrgUnit /> </Publisher> </Publishers> <License>https://creativecommons.org/licenses/by-sa/4.0/</License> <Abstract>This thesis explores synthetic and post-synthetic strategies for tailoring the chemical and physical properties of metal-organic frameworks (MOFs), with a particular emphasis on modulating redox activity, framework composition, and ionic conductivity. The first part of the work focuses on leveraging MOF-embedded polynuclear metal clusters for multi-electron redox chemistry. A square-planar tetramanganese cluster was shown to reversibly interconvert between molecular oxygen and metal-oxo species via a four-electron pathway. This reactivity was then investigated by varying the identity and redox potential of the metal centers within the tetrametal cluster. The Fe(II) and Co(II) analogs reveal distinct metal-specific behavior and provide insight into the tunability of redox-active SBUs within MOFs. Next, post-synthetic cation exchange was employed to access a previously unreported Zn-based MOF, ZnZnBTT, which exhibits significant Zn-ion conductivity due to mobile charge-balancing cations. This material demonstrates the potential of MOFs in next-generation solid-state battery technologies. Finally, the impact of linker electron donicity on cluster structure and reactivity was explored using a new mixed-azolate ligand. Four isostructural MOFs incorporating Co, Ni, Cu, and Cd were synthesized, revealing that the electron-rich pyrazolate groups modulate cluster composition and redox behavior. Notably, CoBTDP exhibits O₂ reactivity, unlike its all-tetrazolate counterpart, underscoring the role of linker design in tuning MOF function. Together, these studies demonstrate how careful control over MOF synthesis and post-synthetic modification can be used to fine-tune redox behavior, framework composition, and ion transport, providing new avenues for the design of functional porous materials.</Abstract> <Access xmlns="http://purl.org/coar/access_right" > </Access> </Publication>