{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/19431"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/19431","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Actinide porphyrin complexes","abstract":"The first bis(porphyrin)actinide complexes have been prepared by reaction of M(NEt$\\sb2$)$\\sb4$ (where M = Th, U) with H$\\sb2$TPP or H$\\sb2$OEP. The coordination geometry of (TPP)$\\sb2$Th is a distorted square-prism where the thorium center is displaced 1.47 A from each of the porphyrin N$\\sb4$ planes; the porphyrin planes are separated by 2.94 A. The porphyrin macrocycles, held in such close proximity, interact electronically as shown by a shift in the porphyrin Soret band to higher energy and unusually facile oxidation processes relative to related monoporphyrin complexes.","abstract_html":"The first bis(porphyrin)actinide complexes have been prepared by reaction of M(NEt$\\sb2$)$\\sb4$ (where M = Th, U) with H$\\sb2$TPP or H$\\sb2$OEP. The coordination geometry of (TPP)$\\sb2$Th is a distorted square-prism where the thorium center is displaced 1.47 A from each of the porphyrin N$\\sb4$ planes; the porphyrin planes are separated by 2.94 A. The porphyrin macrocycles, held in such close proximity, interact electronically as shown by a shift in the porphyrin Soret band to higher energy and unusually facile oxidation processes relative to related monoporphyrin complexes.","abstract_has_math":true,"creators":["Milam, Stanley Nemec"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Kenneth S. Suslick"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2011,"date_issued":"2011-05-07T12:07:18Z","date_published":"2011-05-07T12:07:18Z","updated_at":"2026-07-22T22:25:12Z","subjects":["Chemistry, Inorganic","Chemistry, Nuclear"],"languages":["eng"],"rights":["Copyright 1989 Milam, Stanley Nemec"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9010958","(UMI)AAI9010958"],"render_values":[{"text":"AAI9010958","href":null,"code":true},{"text":"(UMI)AAI9010958","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/19431","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Kenneth S. Suslick"]},{"key":"dc:creator","label":"Author","values":["Milam, Stanley Nemec"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:07:18Z","10000-01-01","1989"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"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":["Chemistry, Inorganic","Chemistry, Nuclear"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1989 Milam, Stanley Nemec"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["AAI9010958","(UMI)AAI9010958","http://hdl.handle.net/2142/19431"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The first bis(porphyrin)actinide complexes have been prepared by reaction of M(NEt$\\sb2$)$\\sb4$ (where M = Th, U) with H$\\sb2$TPP or H$\\sb2$OEP. The coordination geometry of (TPP)$\\sb2$Th is a distorted square-prism where the thorium center is displaced 1.47 A from each of the porphyrin N$\\sb4$ planes; the porphyrin planes are separated by 2.94 A. The porphyrin macrocycles, held in such close proximity, interact electronically as shown by a shift in the porphyrin Soret band to higher energy and unusually facile oxidation processes relative to related monoporphyrin complexes.","Oxidation of (TPP)$\\sb2$M yields porphyrin-based radical cation complexes ((TPP)$\\sb2$M$\\sp+$) (SbCl$\\sb6\\sp-$) and dicationic complexes, ((TPP)$\\sb2$M$\\sp{2+}$) (SbCl$\\sb6\\sp-$) $\\sb2$. The porphyrin planes of ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) are separated by 2.89 A, this separation is slightly less than that of (TPP)$\\sb2$Th.","The EPR spectrum of ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) is that of a simple organic radical (g = 2.0016) while the uranium complex shows unusual signals at g$\\sb{\\rm para}$ = 3.175 and g$\\sb{\\rm perp}$ = 1.343. SQUID measurements on ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) suggest that above 70 K there are thermally populated excited state(s) with f-orbital character. Above 200 K, ((TPP)$\\sb2$U$\\sp+$) (SbCl$\\sb6\\sp-$) apparently adopts S = 3/2 spin state(s), but below 70 K the spin state appears to be S = 1/2. This behavior may be due to antiferromagnetic coupling of the porphyrin radical to the f$\\sp2$ U$\\sp{\\rm IV}$ center.","The dicationic complex ((TPP)$\\sb2$Th$\\sp{2+}$) (SbCl$\\sb6\\sp-$) $\\sb2$ is essentially diamagnetic. This suggests that there is a direct porphyrin-porphyrin interaction that results in a new set of molecular orbitals composed of both porphyrin ligands and perhaps some metal contribution. All of the oxidized complexes have near-IR absorptions due to transitions between these molecular orbitals.","Mono(porphyrin)actinide complexes may be prepared directly from UCl$\\sb4$ or ThCl$\\sb4$. The uranium center of (TPP)UCl$\\sb2$(thf) is displaced 1.29 A from the porphyrin macrocycle. Reaction of Na (OCH(CF$\\sb3$)$\\sb2$) with (TPP)UCl$\\sb2$ in 1,2-dimethoxyethane (dme) yields $\\{$Na(dme)$\\sb3\\sp+\\}\\{$(TPP)U (OCH(CF$\\sb3$)$\\sb2$) $\\sb3\\sp-\\}$. The uranium center of this complex is displaced 1.43 A from the porphyrin macrocycle plane. Reaction of KOC$\\sb6$H$\\sb3$Cl$\\sb2$ with (TPP)UCl$\\sb2$ yields (TPP)U(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$, which has an available coordination site and binds Lewis bases. (TPP)U(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$ reacts with O$\\sb2$ to form the first U$\\sp{\\rm VI}$ porphyrin complex (TPP)U(O)(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$. This oxo complex cannot oxidize PPh$\\sb3$ to OPPh$\\sb3$.","Made available in DSpace on 2011-05-07T12:07:18Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9010958.pdf: 4824008 bytes, checksum: 965618b03f6ae9b6415edd090ecd55b7 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:36:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:15:04-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["Actinide porphyrin complexes"]}]}],"canonical_facts":{"dc:contributor":["Kenneth S. Suslick"],"dc:creator":["Milam, Stanley Nemec"],"dc:date":["2011-05-07T12:07:18Z","10000-01-01","1989"],"dc:description":["The first bis(porphyrin)actinide complexes have been prepared by reaction of M(NEt$\\sb2$)$\\sb4$ (where M = Th, U) with H$\\sb2$TPP or H$\\sb2$OEP. The coordination geometry of (TPP)$\\sb2$Th is a distorted square-prism where the thorium center is displaced 1.47 A from each of the porphyrin N$\\sb4$ planes; the porphyrin planes are separated by 2.94 A. The porphyrin macrocycles, held in such close proximity, interact electronically as shown by a shift in the porphyrin Soret band to higher energy and unusually facile oxidation processes relative to related monoporphyrin complexes.","Oxidation of (TPP)$\\sb2$M yields porphyrin-based radical cation complexes ((TPP)$\\sb2$M$\\sp+$) (SbCl$\\sb6\\sp-$) and dicationic complexes, ((TPP)$\\sb2$M$\\sp{2+}$) (SbCl$\\sb6\\sp-$) $\\sb2$. The porphyrin planes of ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) are separated by 2.89 A, this separation is slightly less than that of (TPP)$\\sb2$Th.","The EPR spectrum of ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) is that of a simple organic radical (g = 2.0016) while the uranium complex shows unusual signals at g$\\sb{\\rm para}$ = 3.175 and g$\\sb{\\rm perp}$ = 1.343. SQUID measurements on ((TPP)$\\sb2$Th$\\sp+$) (SbCl$\\sb6\\sp-$) suggest that above 70 K there are thermally populated excited state(s) with f-orbital character. Above 200 K, ((TPP)$\\sb2$U$\\sp+$) (SbCl$\\sb6\\sp-$) apparently adopts S = 3/2 spin state(s), but below 70 K the spin state appears to be S = 1/2. This behavior may be due to antiferromagnetic coupling of the porphyrin radical to the f$\\sp2$ U$\\sp{\\rm IV}$ center.","The dicationic complex ((TPP)$\\sb2$Th$\\sp{2+}$) (SbCl$\\sb6\\sp-$) $\\sb2$ is essentially diamagnetic. This suggests that there is a direct porphyrin-porphyrin interaction that results in a new set of molecular orbitals composed of both porphyrin ligands and perhaps some metal contribution. All of the oxidized complexes have near-IR absorptions due to transitions between these molecular orbitals.","Mono(porphyrin)actinide complexes may be prepared directly from UCl$\\sb4$ or ThCl$\\sb4$. The uranium center of (TPP)UCl$\\sb2$(thf) is displaced 1.29 A from the porphyrin macrocycle. Reaction of Na (OCH(CF$\\sb3$)$\\sb2$) with (TPP)UCl$\\sb2$ in 1,2-dimethoxyethane (dme) yields $\\{$Na(dme)$\\sb3\\sp+\\}\\{$(TPP)U (OCH(CF$\\sb3$)$\\sb2$) $\\sb3\\sp-\\}$. The uranium center of this complex is displaced 1.43 A from the porphyrin macrocycle plane. Reaction of KOC$\\sb6$H$\\sb3$Cl$\\sb2$ with (TPP)UCl$\\sb2$ yields (TPP)U(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$, which has an available coordination site and binds Lewis bases. (TPP)U(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$ reacts with O$\\sb2$ to form the first U$\\sp{\\rm VI}$ porphyrin complex (TPP)U(O)(OC$\\sb6$H$\\sb3$Cl$\\sb2$)$\\sb2$. This oxo complex cannot oxidize PPh$\\sb3$ to OPPh$\\sb3$.","Made available in DSpace on 2011-05-07T12:07:18Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9010958.pdf: 4824008 bytes, checksum: 965618b03f6ae9b6415edd090ecd55b7 (MD5) Previous issue date: 1989","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:36:54Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:15:04-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["AAI9010958","(UMI)AAI9010958","http://hdl.handle.net/2142/19431"],"dc:language":["eng"],"dc:rights":["Copyright 1989 Milam, Stanley Nemec"],"dc:subject":["Chemistry, Inorganic","Chemistry, Nuclear"],"dc:title":["Actinide porphyrin complexes"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:12Z"}