{"id":{"repo_id":"uic","oai_identifier":"oai:figshare.com:article/32995106"},"canonical_url":"https://search.dev.ndltd.org/etd/uic/oai:figshare.com:article/32995106","repository":{"repo_id":"uic","name":"University of Illinois - Chicago","base_url":"https://api.figshare.com/v2/oai"},"display":{"title":"Harnessing Aluminum Radicals via Heterobimetallic Complexes for Small-molecule Activation","abstract":"Aluminum is the most abundant metal in Earth’s crust, yet its chemistry is often considered limited because it predominantly exists in the thermodynamically stable +3 oxidation state. Accessing the rare +2 oxidation state could enable fundamentally new reactivity, but Al(II) species are typically unstable and prone to rapid decomposition or dimerization. This dissertation develops strategies to generate and stabilize aluminum-centered radicals through ligand design and main-group/transition-metal heterobimetallic cooperativity, enabling aluminum to participate in single-electron processes traditionally associated with transition metals and f-block elements. A central theme of this work is the development of multiple design strategies, including redox non-innocent ligands and strained coordination geometries, to impart biphilic character to aluminum radicals and precisely tune their reactivity, alongside heterobimetallic frameworks that enable the generation of “masked” Al(II) species capable of small-molecule activation. These systems exhibit diverse and controllable behavior, including proton-coupled electron transfer (PCET) processes for activating strong bonds in molecules such as water and ammonia, switchable two-electron frustrated Lewis pair reactivity, photochemically induced radical pathways, and cooperative CO₂ activation through stepwise single-electron mechanisms. These concepts are further extended to multistate redox platforms and ligand-centered diradical frameworks aimed at p-block-based magnetic materials, featuring pyrazine-bridged dialuminum complexes with tunable open-shell character and Al/Cr heterobimetallic systems that display cyclopentadienyl ligand non-innocent reactivity. Collectively, these studies establish aluminum as a viable component in open-shell architectures and molecular magnetic materials, demonstrating that rational ligand and electronic design can unlock unconventional oxidation states and radical reactivity in main-group elements, thereby broadening the scope of sustainable catalysis and functional materials based on earth-abundant metals.","abstract_html":"Aluminum is the most abundant metal in Earth’s crust, yet its chemistry is often considered limited because it predominantly exists in the thermodynamically stable +3 oxidation state. Accessing the rare +2 oxidation state could enable fundamentally new reactivity, but Al(II) species are typically unstable and prone to rapid decomposition or dimerization. This dissertation develops strategies to generate and stabilize aluminum-centered radicals through ligand design and main-group/transition-metal heterobimetallic cooperativity, enabling aluminum to participate in single-electron processes traditionally associated with transition metals and f-block elements. A central theme of this work is the development of multiple design strategies, including redox non-innocent ligands and strained coordination geometries, to impart biphilic character to aluminum radicals and precisely tune their reactivity, alongside heterobimetallic frameworks that enable the generation of “masked” Al(II) species capable of small-molecule activation. These systems exhibit diverse and controllable behavior, including proton-coupled electron transfer (PCET) processes for activating strong bonds in molecules such as water and ammonia, switchable two-electron frustrated Lewis pair reactivity, photochemically induced radical pathways, and cooperative CO₂ activation through stepwise single-electron mechanisms. These concepts are further extended to multistate redox platforms and ligand-centered diradical frameworks aimed at p-block-based magnetic materials, featuring pyrazine-bridged dialuminum complexes with tunable open-shell character and Al/Cr heterobimetallic systems that display cyclopentadienyl ligand non-innocent reactivity. Collectively, these studies establish aluminum as a viable component in open-shell architectures and molecular magnetic materials, demonstrating that rational ligand and electronic design can unlock unconventional oxidation states and radical reactivity in main-group elements, thereby broadening the scope of sustainable catalysis and functional materials based on earth-abundant metals.","abstract_has_math":false,"creators":["Roushan Prakash Singh (11674920)"],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2026,"date_issued":"2026-05-01T00:00:00Z","date_published":"2026-05-01T00:00:00Z","updated_at":"2026-07-27T21:33:48Z","subjects":["Aluminum","Ligands","Metals","Reactivity","Redox reactions"],"languages":[],"rights":["In Copyright","Open Access after 2028-05-01"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://doi.org/10.25417/uic.32995106.v1","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Roushan Prakash Singh (11674920)"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2026-05-01T00:00:00Z"]},{"key":"dc:relation","label":"Dc Relation","values":["https://figshare.com/articles/thesis/Harnessing_Aluminum_Radicals_via_Heterobimetallic_Complexes_for_Small-molecule_Activation/32995106"]},{"key":"dc:type","label":"Dc Type","values":["Text","Thesis"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Aluminum","Ligands","Metals","Reactivity","Redox reactions"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:rights","label":"Dc Rights","values":["In Copyright","Open Access after 2028-05-01"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["10.25417/uic.32995106.v1"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Aluminum is the most abundant metal in Earth’s crust, yet its chemistry is often considered limited because it predominantly exists in the thermodynamically stable +3 oxidation state. Accessing the rare +2 oxidation state could enable fundamentally new reactivity, but Al(II) species are typically unstable and prone to rapid decomposition or dimerization. This dissertation develops strategies to generate and stabilize aluminum-centered radicals through ligand design and main-group/transition-metal heterobimetallic cooperativity, enabling aluminum to participate in single-electron processes traditionally associated with transition metals and f-block elements. A central theme of this work is the development of multiple design strategies, including redox non-innocent ligands and strained coordination geometries, to impart biphilic character to aluminum radicals and precisely tune their reactivity, alongside heterobimetallic frameworks that enable the generation of “masked” Al(II) species capable of small-molecule activation. These systems exhibit diverse and controllable behavior, including proton-coupled electron transfer (PCET) processes for activating strong bonds in molecules such as water and ammonia, switchable two-electron frustrated Lewis pair reactivity, photochemically induced radical pathways, and cooperative CO₂ activation through stepwise single-electron mechanisms. These concepts are further extended to multistate redox platforms and ligand-centered diradical frameworks aimed at p-block-based magnetic materials, featuring pyrazine-bridged dialuminum complexes with tunable open-shell character and Al/Cr heterobimetallic systems that display cyclopentadienyl ligand non-innocent reactivity. Collectively, these studies establish aluminum as a viable component in open-shell architectures and molecular magnetic materials, demonstrating that rational ligand and electronic design can unlock unconventional oxidation states and radical reactivity in main-group elements, thereby broadening the scope of sustainable catalysis and functional materials based on earth-abundant metals."]},{"key":"dc:title","label":"Title","values":["Harnessing Aluminum Radicals via Heterobimetallic Complexes for Small-molecule Activation"]}]}],"canonical_facts":{"dc:creator":["Roushan Prakash Singh (11674920)"],"dc:date":["2026-05-01T00:00:00Z"],"dc:description":["Aluminum is the most abundant metal in Earth’s crust, yet its chemistry is often considered limited because it predominantly exists in the thermodynamically stable +3 oxidation state. Accessing the rare +2 oxidation state could enable fundamentally new reactivity, but Al(II) species are typically unstable and prone to rapid decomposition or dimerization. This dissertation develops strategies to generate and stabilize aluminum-centered radicals through ligand design and main-group/transition-metal heterobimetallic cooperativity, enabling aluminum to participate in single-electron processes traditionally associated with transition metals and f-block elements. A central theme of this work is the development of multiple design strategies, including redox non-innocent ligands and strained coordination geometries, to impart biphilic character to aluminum radicals and precisely tune their reactivity, alongside heterobimetallic frameworks that enable the generation of “masked” Al(II) species capable of small-molecule activation. These systems exhibit diverse and controllable behavior, including proton-coupled electron transfer (PCET) processes for activating strong bonds in molecules such as water and ammonia, switchable two-electron frustrated Lewis pair reactivity, photochemically induced radical pathways, and cooperative CO₂ activation through stepwise single-electron mechanisms. These concepts are further extended to multistate redox platforms and ligand-centered diradical frameworks aimed at p-block-based magnetic materials, featuring pyrazine-bridged dialuminum complexes with tunable open-shell character and Al/Cr heterobimetallic systems that display cyclopentadienyl ligand non-innocent reactivity. Collectively, these studies establish aluminum as a viable component in open-shell architectures and molecular magnetic materials, demonstrating that rational ligand and electronic design can unlock unconventional oxidation states and radical reactivity in main-group elements, thereby broadening the scope of sustainable catalysis and functional materials based on earth-abundant metals."],"dc:identifier":["10.25417/uic.32995106.v1"],"dc:relation":["https://figshare.com/articles/thesis/Harnessing_Aluminum_Radicals_via_Heterobimetallic_Complexes_for_Small-molecule_Activation/32995106"],"dc:rights":["In Copyright","Open Access after 2028-05-01"],"dc:subject":["Aluminum","Ligands","Metals","Reactivity","Redox reactions"],"dc:title":["Harnessing Aluminum Radicals via Heterobimetallic Complexes for Small-molecule Activation"],"dc:type":["Text","Thesis"]},"updated_at":"2026-07-27T21:33:48Z"}