{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/117830"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/117830","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Dye-sensitized cobalt cubane: ultrafast photophysics probed by transient XUV spectroscopy","abstract":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-04-12 without embargo terms","abstract_html":"Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-04-12 without embargo terms","abstract_has_math":false,"creators":["Shari'ati, Yusef A"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Vura-Weis, Josh","van der Veen, Renske","Fout, Alison","Olshansky, Lisa"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2022,"date_issued":"2022-12","date_published":"2022-12","updated_at":"2026-07-22T22:24:56Z","subjects":["Ultrafast Spectroscopy","Extreme Ultraviolet","Water Oxidation Catalysis","Photoinduced Electron Transfer","Cobalt Oxide","Cubane","Perylene Diimide"],"languages":["en","eng"],"rights":["Copyright 2022 Yusef Shari'ati"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/117830","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Vura-Weis, Josh","van der Veen, Renske","Fout, Alison","Olshansky, Lisa"]},{"key":"dc:creator","label":"Author","values":["Shari'ati, Yusef A"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2022-12","2022-12-02"]},{"key":"dc:type","label":"Dc Type","values":["text","Thesis"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Ultrafast Spectroscopy","Extreme Ultraviolet","Water Oxidation Catalysis","Photoinduced Electron Transfer","Cobalt Oxide","Cubane","Perylene Diimide"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2022 Yusef Shari'ati"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/117830"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-04-12 without embargo terms","The student, Yusef Shari'ati, accepted the attached license on 2022-12-02 at 14:44.","The student, Yusef Shari'ati, submitted this Dissertation for approval on 2022-12-02 at 14:51.","This Dissertation was approved for publication on 2022-12-02 at 15:06.","DSpace SAF Submission Ingestion Package generated from Vireo submission #18744 on 2023-04-12 at 07:37:49","The production of renewable solar fuels on a global scale requires the development of water oxidation catalysts from Earth-abundant elements. The tetrametallic oxo-cluster, [CoIII4O4](OAc)4(py)4 (OAc = acetate, py = pyridine), Q1, is a promising molecular compound that has attracted significant interest due to its provocative “cubane” structure and as an especially apposite molecular model for heterogeneous CoOx-based water oxidation catalysis. This work seeks to provide understanding of the electronic structure of Q1 in its neutral and oxidized, ground and excited states. To that end the technique of femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used as a metal-sensitive probe in the extreme ultraviolet (XUV) region of the electromagnetic spectrum near 50-90 eV. A new sample preparation method is developed for the production of high-quality thin films suitable for XUV spectroscopy. Both static and transient spectra are collected and are interpreted in terms of oxidation state, spin state, and hole delocalization within the structure by comparison with ligand-field multiplet simulations. In this work is also presented the means of cubane photosensitization using perylene diimide chromophores. Optical transient absorption spectroscopy is used to verify successful electron transfer, and evidence for energy transfer is also observed. It is further found that Q1 ligand-field excitation with green visible light results in rapid singlet→quintet intersystem crossing (ISC) in 38 fs. The merits of exponential vs. non-exponential kinetics to describe these dynamics are discussed, as well as the greater implications for ultrafast ISC in transition metal complexes."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Dye-sensitized cobalt cubane: ultrafast photophysics probed by transient XUV spectroscopy"]}]}],"canonical_facts":{"dc:contributor":["Vura-Weis, Josh","van der Veen, Renske","Fout, Alison","Olshansky, Lisa"],"dc:creator":["Shari'ati, Yusef A"],"dc:date":["2022-12","2022-12-02"],"dc:description":["Submission original under an indefinite embargo labeled 'Open Access'. The submission was exported from vireo on 2023-04-12 without embargo terms","The student, Yusef Shari'ati, accepted the attached license on 2022-12-02 at 14:44.","The student, Yusef Shari'ati, submitted this Dissertation for approval on 2022-12-02 at 14:51.","This Dissertation was approved for publication on 2022-12-02 at 15:06.","DSpace SAF Submission Ingestion Package generated from Vireo submission #18744 on 2023-04-12 at 07:37:49","The production of renewable solar fuels on a global scale requires the development of water oxidation catalysts from Earth-abundant elements. The tetrametallic oxo-cluster, [CoIII4O4](OAc)4(py)4 (OAc = acetate, py = pyridine), Q1, is a promising molecular compound that has attracted significant interest due to its provocative “cubane” structure and as an especially apposite molecular model for heterogeneous CoOx-based water oxidation catalysis. This work seeks to provide understanding of the electronic structure of Q1 in its neutral and oxidized, ground and excited states. To that end the technique of femtosecond M2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy is used as a metal-sensitive probe in the extreme ultraviolet (XUV) region of the electromagnetic spectrum near 50-90 eV. A new sample preparation method is developed for the production of high-quality thin films suitable for XUV spectroscopy. Both static and transient spectra are collected and are interpreted in terms of oxidation state, spin state, and hole delocalization within the structure by comparison with ligand-field multiplet simulations. In this work is also presented the means of cubane photosensitization using perylene diimide chromophores. Optical transient absorption spectroscopy is used to verify successful electron transfer, and evidence for energy transfer is also observed. It is further found that Q1 ligand-field excitation with green visible light results in rapid singlet→quintet intersystem crossing (ISC) in 38 fs. The merits of exponential vs. non-exponential kinetics to describe these dynamics are discussed, as well as the greater implications for ultrafast ISC in transition metal complexes."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/117830"],"dc:language":["en","eng"],"dc:rights":["Copyright 2022 Yusef Shari'ati"],"dc:subject":["Ultrafast Spectroscopy","Extreme Ultraviolet","Water Oxidation Catalysis","Photoinduced Electron Transfer","Cobalt Oxide","Cubane","Perylene Diimide"],"dc:title":["Dye-sensitized cobalt cubane: ultrafast photophysics probed by transient XUV spectroscopy"],"dc:type":["text","Thesis"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:24:56Z"}