{"id":{"repo_id":"ohiolink","oai_identifier":"oai:etd.ohiolink.edu:osu1366111201"},"canonical_url":"https://search.dev.ndltd.org/etd/ohiolink/oai:etd.ohiolink.edu:osu1366111201","repository":{"repo_id":"ohiolink","name":"OhioLINK","base_url":"https://etd.ohiolink.edu/acprod/odb_etd/ws/oai/oai"},"display":{"title":"Photochemistry and Photophysics of Octahedral Ruthenium Complexes","abstract":"The photo-induced ligand loss of the complexes [Ru(tpy)(AN)3]2+ and cis-[Ru(tpy)(AN)2Cl]+ (tpy = 2,2`:6`2``-terpyridine) and [Ru(tpy)(5CNU)3]2+ was studied in water and in CH2Cl2 in the presence of chloride from tetrabutylammonium chloride (TBACl). [Ru(tpy)(5CNU)3]2+ is not soluble in CH2Cl2. Photolysis in CH2Cl2 in the presence of chloride ions leads to the dichloro photoproduct trans-[Ru(tpy)(AN)Cl2], and photolysis in water led to the diaqua photoproduct trans-[Ru(tpy)(AN)(H2O)2]2+ or trans-[Ru(tpy)(5CNU)(H2O)2]2+. The two axial ligands are replaced, while the equatorial ligand remains coordinated to the metal. For cis-[Ru(tpy)(AN)3]2+ and [Ru(tpy)(5CNU)3]2+ the axial ligands were replaced in a step-wise fashion, forming an intermediate with one axial acetonitrile ligand. All three complexes were shown to bind to DNA upon photolysis by gel electrophoresis, but not in the absence of light, indicating potential as anti-tumor agents for use in photodynamic therapy (PDT). cis-[Ru(tpy)(AN)2Cl]+ has a higher quantum yield of ligand substitution and a lower energy metal to ligand charge transfer (MLCT) transition showing binding to DNA when irradiated at 650 nm, within the ideal PDT window of 600-850 nm.The low temperature emission and photolysis of [Ru(bpy)3]2+, cis-[Ru(bpy)2(AN)2]2+, cis-[Ru(bpy)2(MeBN)2]2+, and cis-[Ru(bpy)2(py)2]2+ was studied to explore their excited state properties. The emission of [Ru(bpy)3]2+ is known to take place from the 3MLCT state, with a temperature dependence resulting from a thermally accessible non-emissive triplet ligand field state higher in energy than the 3MLCT state. A decrease in emission quantum yield and comparable increase in the quantum yield of photolysis is observed for [Ru(bpy)3]2+ with increasing temperature. This behavior led to the conclusion that the population of the 3LF from the 3MLCT state preceded photosubstitution. The temperature dependence of the emission of the related compounds cis-[Ru(bpy)2L2]2+, where L is AN, MeBN and py, was found to be different from the temperature dependence of the photolysis, suggesting that the photosubstitution proceeds through a different mechanism. One possibility is that the 3LF state is populated directly from the initially excited state and does not require population through the 3MLCT state.","abstract_html":"The photo-induced ligand loss of the complexes [Ru(tpy)(AN)<sub>3</sub>]<sup>2+</sup> and cis-[Ru(tpy)(AN)<sub>2</sub>Cl]<sup>+</sup> (tpy = 2,2`:6`2``-terpyridine) and [Ru(tpy)(5CNU)<sub>3</sub>]<sup>2+</sup> was studied in water and in CH<sub>2</sub>Cl<sub>2</sub> in the presence of chloride from tetrabutylammonium chloride (TBACl). [Ru(tpy)(5CNU)<sub>3</sub>]<sup>2+</sup> is not soluble in CH<sub>2</sub>Cl<sub>2</sub>. Photolysis in CH<sub>2</sub>Cl<sub>2</sub> in the presence of chloride ions leads to the dichloro photoproduct trans-[Ru(tpy)(AN)Cl<sub>2</sub>], and photolysis in water led to the diaqua photoproduct trans-[Ru(tpy)(AN)(H2O)<sub>2</sub>]<sup>2+</sup> or trans-[Ru(tpy)(5CNU)(H2O)<sub>2</sub>]<sup>2+</sup>. The two axial ligands are replaced, while the equatorial ligand remains coordinated to the metal. For cis-[Ru(tpy)(AN)<sub>3</sub>]<sup>2+</sup> and [Ru(tpy)(5CNU)<sub>3</sub>]<sup>2+</sup> the axial ligands were replaced in a step-wise fashion, forming an intermediate with one axial acetonitrile ligand. All three complexes were shown to bind to DNA upon photolysis by gel electrophoresis, but not in the absence of light, indicating potential as anti-tumor agents for use in photodynamic therapy (PDT). cis-[Ru(tpy)(AN)<sub>2</sub>Cl]<sup>+</sup> has a higher quantum yield of ligand substitution and a lower energy metal to ligand charge transfer (MLCT) transition showing binding to DNA when irradiated at 650 nm, within the ideal PDT window of 600-850 nm.The low temperature emission and photolysis of [Ru(bpy)<sub>3</sub>]<sup>2+</sup>, cis-[Ru(bpy)<sub>2</sub>(AN)<sub>2</sub>]<sup>2+</sup>, cis-[Ru(bpy)<sub>2</sub>(MeBN)<sub>2</sub>]<sup>2+</sup>, and cis-[Ru(bpy)<sub>2</sub>(py)<sub>2</sub>]<sup>2+</sup> was studied to explore their excited state properties. The emission of [Ru(bpy)<sub>3</sub>]<sup>2+</sup> is known to take place from the <sup>3</sup>MLCT state, with a temperature dependence resulting from a thermally accessible non-emissive triplet ligand field state higher in energy than the <sup>3</sup>MLCT state. A decrease in emission quantum yield and comparable increase in the quantum yield of photolysis is observed for [Ru(bpy)<sub>3</sub>]<sup>2+</sup> with increasing temperature. This behavior led to the conclusion that the population of the <sup>3</sup>LF from the <sup>3</sup>MLCT state preceded photosubstitution. The temperature dependence of the emission of the related compounds cis-[Ru(bpy)<sub>2</sub>L<sub>2</sub>]<sup>2+</sup>, where L is AN, MeBN and py, was found to be different from the temperature dependence of the photolysis, suggesting that the photosubstitution proceeds through a different mechanism. One possibility is that the <sup>3</sup>LF state is populated directly from the initially excited state and does not require population through the <sup>3</sup>MLCT state.","abstract_has_math":false,"creators":["Sgambellone, Mark Allan"],"institution":"The Ohio State University","degree_name":"Doctor of Philosophy","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Turro, Claudia"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-08-09","date_published":"2013-08-09","updated_at":"2026-07-24T03:37:46Z","subjects":["Chemistry","Ruthenium","photolysis","photochemistry","Photodynamic Therapy","PDT"],"languages":["English"],"rights":["unrestricted","This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://rave.ohiolink.edu/etdc/view?acc_num=osu1366111201","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Turro, Claudia"]},{"key":"dc:creator","label":"Author","values":["Sgambellone, Mark Allan"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-08-09"]},{"key":"dc:publisher","label":"Institution","values":["The Ohio State University / OhioLINK"]},{"key":"dc:type","label":"Dc Type","values":["Electronic Thesis or Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["The Ohio State University"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Ruthenium","photolysis","photochemistry","Photodynamic Therapy","PDT"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:rights","label":"Dc Rights","values":["unrestricted","This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://rave.ohiolink.edu/etdc/view?acc_num=osu1366111201"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The photo-induced ligand loss of the complexes [Ru(tpy)(AN)3]2+ and cis-[Ru(tpy)(AN)2Cl]+ (tpy = 2,2`:6`2``-terpyridine) and [Ru(tpy)(5CNU)3]2+ was studied in water and in CH2Cl2 in the presence of chloride from tetrabutylammonium chloride (TBACl). [Ru(tpy)(5CNU)3]2+ is not soluble in CH2Cl2. Photolysis in CH2Cl2 in the presence of chloride ions leads to the dichloro photoproduct trans-[Ru(tpy)(AN)Cl2], and photolysis in water led to the diaqua photoproduct trans-[Ru(tpy)(AN)(H2O)2]2+ or trans-[Ru(tpy)(5CNU)(H2O)2]2+. The two axial ligands are replaced, while the equatorial ligand remains coordinated to the metal. For cis-[Ru(tpy)(AN)3]2+ and [Ru(tpy)(5CNU)3]2+ the axial ligands were replaced in a step-wise fashion, forming an intermediate with one axial acetonitrile ligand. All three complexes were shown to bind to DNA upon photolysis by gel electrophoresis, but not in the absence of light, indicating potential as anti-tumor agents for use in photodynamic therapy (PDT). cis-[Ru(tpy)(AN)2Cl]+ has a higher quantum yield of ligand substitution and a lower energy metal to ligand charge transfer (MLCT) transition showing binding to DNA when irradiated at 650 nm, within the ideal PDT window of 600-850 nm.The low temperature emission and photolysis of [Ru(bpy)3]2+, cis-[Ru(bpy)2(AN)2]2+, cis-[Ru(bpy)2(MeBN)2]2+, and cis-[Ru(bpy)2(py)2]2+ was studied to explore their excited state properties. The emission of [Ru(bpy)3]2+ is known to take place from the 3MLCT state, with a temperature dependence resulting from a thermally accessible non-emissive triplet ligand field state higher in energy than the 3MLCT state. A decrease in emission quantum yield and comparable increase in the quantum yield of photolysis is observed for [Ru(bpy)3]2+ with increasing temperature. This behavior led to the conclusion that the population of the 3LF from the 3MLCT state preceded photosubstitution. The temperature dependence of the emission of the related compounds cis-[Ru(bpy)2L2]2+, where L is AN, MeBN and py, was found to be different from the temperature dependence of the photolysis, suggesting that the photosubstitution proceeds through a different mechanism. One possibility is that the 3LF state is populated directly from the initially excited state and does not require population through the 3MLCT state."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","p.162","6.89 MB"]},{"key":"dc:title","label":"Title","values":["Photochemistry and Photophysics of Octahedral Ruthenium Complexes"]}]}],"canonical_facts":{"dc:contributor":["Turro, Claudia"],"dc:creator":["Sgambellone, Mark Allan"],"dc:date":["2013-08-09"],"dc:description":["The photo-induced ligand loss of the complexes [Ru(tpy)(AN)3]2+ and cis-[Ru(tpy)(AN)2Cl]+ (tpy = 2,2`:6`2``-terpyridine) and [Ru(tpy)(5CNU)3]2+ was studied in water and in CH2Cl2 in the presence of chloride from tetrabutylammonium chloride (TBACl). [Ru(tpy)(5CNU)3]2+ is not soluble in CH2Cl2. Photolysis in CH2Cl2 in the presence of chloride ions leads to the dichloro photoproduct trans-[Ru(tpy)(AN)Cl2], and photolysis in water led to the diaqua photoproduct trans-[Ru(tpy)(AN)(H2O)2]2+ or trans-[Ru(tpy)(5CNU)(H2O)2]2+. The two axial ligands are replaced, while the equatorial ligand remains coordinated to the metal. For cis-[Ru(tpy)(AN)3]2+ and [Ru(tpy)(5CNU)3]2+ the axial ligands were replaced in a step-wise fashion, forming an intermediate with one axial acetonitrile ligand. All three complexes were shown to bind to DNA upon photolysis by gel electrophoresis, but not in the absence of light, indicating potential as anti-tumor agents for use in photodynamic therapy (PDT). cis-[Ru(tpy)(AN)2Cl]+ has a higher quantum yield of ligand substitution and a lower energy metal to ligand charge transfer (MLCT) transition showing binding to DNA when irradiated at 650 nm, within the ideal PDT window of 600-850 nm.The low temperature emission and photolysis of [Ru(bpy)3]2+, cis-[Ru(bpy)2(AN)2]2+, cis-[Ru(bpy)2(MeBN)2]2+, and cis-[Ru(bpy)2(py)2]2+ was studied to explore their excited state properties. The emission of [Ru(bpy)3]2+ is known to take place from the 3MLCT state, with a temperature dependence resulting from a thermally accessible non-emissive triplet ligand field state higher in energy than the 3MLCT state. A decrease in emission quantum yield and comparable increase in the quantum yield of photolysis is observed for [Ru(bpy)3]2+ with increasing temperature. This behavior led to the conclusion that the population of the 3LF from the 3MLCT state preceded photosubstitution. The temperature dependence of the emission of the related compounds cis-[Ru(bpy)2L2]2+, where L is AN, MeBN and py, was found to be different from the temperature dependence of the photolysis, suggesting that the photosubstitution proceeds through a different mechanism. One possibility is that the 3LF state is populated directly from the initially excited state and does not require population through the 3MLCT state."],"dc:format":["application/pdf","p.162","6.89 MB"],"dc:identifier":["http://rave.ohiolink.edu/etdc/view?acc_num=osu1366111201"],"dc:language":["English"],"dc:publisher":["The Ohio State University / OhioLINK"],"dc:rights":["unrestricted","This thesis or dissertation is protected by copyright: some rights reserved. It is licensed for use under a Creative Commons license. Specific terms and permissions are available from this document's record in the OhioLINK ETD Center."],"dc:subject":["Chemistry","Ruthenium","photolysis","photochemistry","Photodynamic Therapy","PDT"],"dc:title":["Photochemistry and Photophysics of Octahedral Ruthenium Complexes"],"dc:type":["Electronic Thesis or Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["The Ohio State University"]},"updated_at":"2026-07-24T03:37:46Z"}