{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/110654"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/110654","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Ultrafast extreme ultraviolet spectroscopy of transition metal dithiolate coordination complexes","abstract":"Transient tabletop M-edge x-ray absorption near edge structure (XANES) spectroscopy using extreme ultraviolet (XUV) light is used as a tool to interrogate the evolution of the metal center in a series of transition metal dithiolate complexes. The behavior of these molecules after absorption of light has implications for the development of catalysts and photosensitizers using earth-abundant transition metals. The cobalt dithiolene complex, [Co(bdt)2]- (bdt = 1,2-benzendithiolate), is primarily known for its ligand-noninnocence and participation in the catalytic production of hydrogen. After excitation of [Co(bdt)2]- with visible light, its relaxation dynamics are tracked with a combination of optical and transient M-edge XANES spectroscopic techniques that allow for the identification of a ligand-to-metal charge transfer (LMCT) excited state whose spin can be determined by comparison to semi-empirical ligand field multiplet calculations. The combination of optical and x-ray techniques is crucial to identifying relaxation processes that affect predominantly either the metal or the ligand. NEVPT2 calculations are used to understand its optical absorption spectrum and rationalize the timescale by which the molecule relaxes to the ground state. A set of three of cobalt tris(dithiolate) complexes with varying ligand field strength have been studied using optical transient absorption spectroscopy which shows a difference of a factor of at least ten in their excited state lifetimes. Understanding the origin of this change is important to further extending the lifetimes of photosensitizers. The sensitivity of M-edge XANES spectroscopy to the oxidation and spin state of a metal enabled the identification of the excited states involved in the relaxation of all three complexes. The contribution of a long-lived charge transfer state was ruled out and the final excited state was determined to be a 5T state. Finally, a nickel dithiocarbamate complex, Ni(dedtc)2 (dedtc = diethyldithiocarbamate, S2CNEt2) was studied as a simple analogue of a square planar nickel-centered hydrogen catalyst. Examination of this complex and the equivalent copper and zinc complexes reveal new phenomena in XUV spectroscopy, including dependence of the ligand absorbance on the metal center and observation of a ligand-based change in absorbance beneath the nickel M-edge after LMCT excitation.","abstract_html":"Transient tabletop M-edge x-ray absorption near edge structure (XANES) spectroscopy using extreme ultraviolet (XUV) light is used as a tool to interrogate the evolution of the metal center in a series of transition metal dithiolate complexes. The behavior of these molecules after absorption of light has implications for the development of catalysts and photosensitizers using earth-abundant transition metals. The cobalt dithiolene complex, [Co(bdt)2]- (bdt = 1,2-benzendithiolate), is primarily known for its ligand-noninnocence and participation in the catalytic production of hydrogen. After excitation of [Co(bdt)2]- with visible light, its relaxation dynamics are tracked with a combination of optical and transient M-edge XANES spectroscopic techniques that allow for the identification of a ligand-to-metal charge transfer (LMCT) excited state whose spin can be determined by comparison to semi-empirical ligand field multiplet calculations. The combination of optical and x-ray techniques is crucial to identifying relaxation processes that affect predominantly either the metal or the ligand. NEVPT2 calculations are used to understand its optical absorption spectrum and rationalize the timescale by which the molecule relaxes to the ground state. A set of three of cobalt tris(dithiolate) complexes with varying ligand field strength have been studied using optical transient absorption spectroscopy which shows a difference of a factor of at least ten in their excited state lifetimes. Understanding the origin of this change is important to further extending the lifetimes of photosensitizers. The sensitivity of M-edge XANES spectroscopy to the oxidation and spin state of a metal enabled the identification of the excited states involved in the relaxation of all three complexes. The contribution of a long-lived charge transfer state was ruled out and the final excited state was determined to be a 5T state. Finally, a nickel dithiocarbamate complex, Ni(dedtc)2 (dedtc = diethyldithiocarbamate, S2CNEt2) was studied as a simple analogue of a square planar nickel-centered hydrogen catalyst. Examination of this complex and the equivalent copper and zinc complexes reveal new phenomena in XUV spectroscopy, including dependence of the ligand absorbance on the metal center and observation of a ligand-based change in absorbance beneath the nickel M-edge after LMCT excitation.","abstract_has_math":false,"creators":["Benke, Kristopher"],"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","Dlott, Dana D","Lu, Yi","van der Veen, Renske"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2021,"date_issued":"2021-09-17T02:34:23Z","date_published":"2021-09-17T02:34:23Z","updated_at":"2026-07-22T22:24:52Z","subjects":["M-edge XANES spectroscopy","ultrafast spectroscopy","transition metal photophysics","ligand noninnocence","photosensitizers"],"languages":["en"],"rights":["Copyright 2021 Kristopher Benke"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/2142/110654","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Vura-Weis, Josh","Dlott, Dana D","Lu, Yi","van der Veen, Renske"]},{"key":"dc:creator","label":"Author","values":["Benke, Kristopher"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2021-09-17T02:34:23Z","2023-09-17T02:34:57Z","2021-04-14","2021-05"]},{"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":["M-edge XANES spectroscopy","ultrafast spectroscopy","transition metal photophysics","ligand noninnocence","photosensitizers"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2021 Kristopher Benke"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/110654"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Transient tabletop M-edge x-ray absorption near edge structure (XANES) spectroscopy using extreme ultraviolet (XUV) light is used as a tool to interrogate the evolution of the metal center in a series of transition metal dithiolate complexes. The behavior of these molecules after absorption of light has implications for the development of catalysts and photosensitizers using earth-abundant transition metals. The cobalt dithiolene complex, [Co(bdt)2]- (bdt = 1,2-benzendithiolate), is primarily known for its ligand-noninnocence and participation in the catalytic production of hydrogen. After excitation of [Co(bdt)2]- with visible light, its relaxation dynamics are tracked with a combination of optical and transient M-edge XANES spectroscopic techniques that allow for the identification of a ligand-to-metal charge transfer (LMCT) excited state whose spin can be determined by comparison to semi-empirical ligand field multiplet calculations. The combination of optical and x-ray techniques is crucial to identifying relaxation processes that affect predominantly either the metal or the ligand. NEVPT2 calculations are used to understand its optical absorption spectrum and rationalize the timescale by which the molecule relaxes to the ground state. A set of three of cobalt tris(dithiolate) complexes with varying ligand field strength have been studied using optical transient absorption spectroscopy which shows a difference of a factor of at least ten in their excited state lifetimes. Understanding the origin of this change is important to further extending the lifetimes of photosensitizers. The sensitivity of M-edge XANES spectroscopy to the oxidation and spin state of a metal enabled the identification of the excited states involved in the relaxation of all three complexes. The contribution of a long-lived charge transfer state was ruled out and the final excited state was determined to be a 5T state. Finally, a nickel dithiocarbamate complex, Ni(dedtc)2 (dedtc = diethyldithiocarbamate, S2CNEt2) was studied as a simple analogue of a square planar nickel-centered hydrogen catalyst. Examination of this complex and the equivalent copper and zinc complexes reveal new phenomena in XUV spectroscopy, including dependence of the ligand absorbance on the metal center and observation of a ligand-based change in absorbance beneath the nickel M-edge after LMCT excitation.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-05-01","The student, Kristopher Benke, accepted the attached license on 2021-04-12 at 10:11.","The student, Kristopher Benke, submitted this Dissertation for approval on 2021-04-12 at 10:46.","This Dissertation was approved for publication on 2021-04-14 at 11:42.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16283 on 2021-09-16 at 17:02:51","Made available in DSpace on 2021-09-17T02:34:23Z (GMT). No. of bitstreams: 3 BENKE-DISSERTATION-2021.pdf: 2425264 bytes, checksum: 1309f977d92270d74397cd3146a8dc91 (MD5) Benke_Kristopher_Dissertation.docx: 11158473 bytes, checksum: af803d0e32292daaea82fd2150cede26 (MD5) LICENSE.txt: 4213 bytes, checksum: e4b94f96dec9482c464d7086c4182278 (MD5) Previous issue date: 2021-04-14","Embargo set by: Seth Robbins for item 118497 Lift date: 2023-09-17T02:34:57Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only"]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Ultrafast extreme ultraviolet spectroscopy of transition metal dithiolate coordination complexes"]}]}],"canonical_facts":{"dc:contributor":["Vura-Weis, Josh","Dlott, Dana D","Lu, Yi","van der Veen, Renske"],"dc:creator":["Benke, Kristopher"],"dc:date":["2021-09-17T02:34:23Z","2023-09-17T02:34:57Z","2021-04-14","2021-05"],"dc:description":["Transient tabletop M-edge x-ray absorption near edge structure (XANES) spectroscopy using extreme ultraviolet (XUV) light is used as a tool to interrogate the evolution of the metal center in a series of transition metal dithiolate complexes. The behavior of these molecules after absorption of light has implications for the development of catalysts and photosensitizers using earth-abundant transition metals. The cobalt dithiolene complex, [Co(bdt)2]- (bdt = 1,2-benzendithiolate), is primarily known for its ligand-noninnocence and participation in the catalytic production of hydrogen. After excitation of [Co(bdt)2]- with visible light, its relaxation dynamics are tracked with a combination of optical and transient M-edge XANES spectroscopic techniques that allow for the identification of a ligand-to-metal charge transfer (LMCT) excited state whose spin can be determined by comparison to semi-empirical ligand field multiplet calculations. The combination of optical and x-ray techniques is crucial to identifying relaxation processes that affect predominantly either the metal or the ligand. NEVPT2 calculations are used to understand its optical absorption spectrum and rationalize the timescale by which the molecule relaxes to the ground state. A set of three of cobalt tris(dithiolate) complexes with varying ligand field strength have been studied using optical transient absorption spectroscopy which shows a difference of a factor of at least ten in their excited state lifetimes. Understanding the origin of this change is important to further extending the lifetimes of photosensitizers. The sensitivity of M-edge XANES spectroscopy to the oxidation and spin state of a metal enabled the identification of the excited states involved in the relaxation of all three complexes. The contribution of a long-lived charge transfer state was ruled out and the final excited state was determined to be a 5T state. Finally, a nickel dithiocarbamate complex, Ni(dedtc)2 (dedtc = diethyldithiocarbamate, S2CNEt2) was studied as a simple analogue of a square planar nickel-centered hydrogen catalyst. Examination of this complex and the equivalent copper and zinc complexes reveal new phenomena in XUV spectroscopy, including dependence of the ligand absorbance on the metal center and observation of a ligand-based change in absorbance beneath the nickel M-edge after LMCT excitation.","Submission published under a 24 month embargo labeled 'U of I Access', the embargo will last until 2023-05-01","The student, Kristopher Benke, accepted the attached license on 2021-04-12 at 10:11.","The student, Kristopher Benke, submitted this Dissertation for approval on 2021-04-12 at 10:46.","This Dissertation was approved for publication on 2021-04-14 at 11:42.","DSpace SAF Submission Ingestion Package generated from Vireo submission #16283 on 2021-09-16 at 17:02:51","Made available in DSpace on 2021-09-17T02:34:23Z (GMT). No. of bitstreams: 3 BENKE-DISSERTATION-2021.pdf: 2425264 bytes, checksum: 1309f977d92270d74397cd3146a8dc91 (MD5) Benke_Kristopher_Dissertation.docx: 11158473 bytes, checksum: af803d0e32292daaea82fd2150cede26 (MD5) LICENSE.txt: 4213 bytes, checksum: e4b94f96dec9482c464d7086c4182278 (MD5) Previous issue date: 2021-04-14","Embargo set by: Seth Robbins for item 118497 Lift date: 2023-09-17T02:34:57Z Reason: Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","Author requested U of Illinois access only (OA after 2yrs) in Vireo ETD system","U of I Only"],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/2142/110654"],"dc:language":["en"],"dc:rights":["Copyright 2021 Kristopher Benke"],"dc:subject":["M-edge XANES spectroscopy","ultrafast spectroscopy","transition metal photophysics","ligand noninnocence","photosensitizers"],"dc:title":["Ultrafast extreme ultraviolet spectroscopy of transition metal dithiolate coordination complexes"],"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":"2026-07-22T22:24:52Z"}