{"id":{"repo_id":"mit","oai_identifier":"oai:dspace.mit.edu:1721.1/162333"},"canonical_url":"https://search.dev.ndltd.org/etd/mit/oai:dspace.mit.edu:1721.1/162333","repository":{"repo_id":"mit","name":"MIT","base_url":"https://dspace.mit.edu/oai/request"},"display":{"title":"Synthetic and Post-Synthetic Methods towards Fine Tuning the Chemical and Physical Properties of Metal-Organic Frameworks","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_html":"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_has_math":false,"creators":["Iliescu, Andrei"],"institution":"Massachusetts Institute of Technology","degree_name":"Doctoral","degree_level":null,"degree_discipline":null,"degree_department":"Massachusetts Institute of Technology. Department of Chemistry","school":null,"contributors":[],"advisors":["Dincă, Mircea"],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-05","date_published":"2025-05","updated_at":"2026-07-22T22:21:24Z","subjects":[],"languages":[],"rights":["Attribution-ShareAlike 4.0 International (CC BY-SA 4.0)","Copyright retained by author(s)"],"rights_urls":["https://creativecommons.org/licenses/by-sa/4.0/"],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/1721.1/162333","outbound_label":"Handle","outbound_source":"dc:identifier.uri"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor.advisor","label":"Advisor","values":["Dincă, Mircea"]},{"key":"dc:contributor.department","label":"Department","values":["Massachusetts Institute of Technology. Department of Chemistry"]},{"key":"dc:creator","label":"Author","values":["Iliescu, Andrei"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date.accessioned","label":"Dc Date Accessioned","values":["2025-08-11T14:19:07Z"]},{"key":"dc:date.available","label":"Dc Date Available","values":["2025-08-11T14:19:07Z"]},{"key":"dc:date.issued","label":"Date","values":["2025-05"]},{"key":"dc:publisher","label":"Institution","values":["Massachusetts Institute of Technology"]},{"key":"dc:type","label":"Dc Type","values":["Thesis"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctoral","Doctor of Philosophy"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["Attribution-ShareAlike 4.0 International (CC BY-SA 4.0)","Copyright retained by author(s)"]},{"key":"dc:rights.uri","label":"Rights URI","values":["https://creativecommons.org/licenses/by-sa/4.0/"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier.uri","label":"Identifier URI","values":["https://hdl.handle.net/1721.1/162333"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["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."]},{"key":"dc:description.degree","label":"Dc Description Degree","values":["Ph.D."]},{"key":"dc:title","label":"Title","values":["Synthetic and Post-Synthetic Methods towards Fine Tuning the Chemical and Physical Properties of Metal-Organic Frameworks"]}]}],"canonical_facts":{"dc:contributor.advisor":["Dincă, Mircea"],"dc:contributor.department":["Massachusetts Institute of Technology. Department of Chemistry"],"dc:creator":["Iliescu, Andrei"],"dc:date.accessioned":["2025-08-11T14:19:07Z"],"dc:date.available":["2025-08-11T14:19:07Z"],"dc:date.issued":["2025-05"],"dc:description.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."],"dc:description.degree":["Ph.D."],"dc:identifier.uri":["https://hdl.handle.net/1721.1/162333"],"dc:publisher":["Massachusetts Institute of Technology"],"dc:rights":["Attribution-ShareAlike 4.0 International (CC BY-SA 4.0)","Copyright retained by author(s)"],"dc:rights.uri":["https://creativecommons.org/licenses/by-sa/4.0/"],"dc:title":["Synthetic and Post-Synthetic Methods towards Fine Tuning the Chemical and Physical Properties of Metal-Organic Frameworks"],"dc:type":["Thesis"],"thesis:degree_name":["Doctoral","Doctor of Philosophy"]},"updated_at":"2026-07-22T22:21:24Z"}