{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/70302"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/70302","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Electron Transfer in a Series of Mixed-Valence Copper(ii)-Copper(i) Complexes (Epr, Electrochemistry, It Bands, Magnetism)","abstract":"Three series of mixed-valence copper(II)-copper(I) complexes of macrocyclic ligands have been prepared to examine systematically the factors affecting intramolecular electron transfer. The mixed-valence complexes are similar to the one prepared by Gagne et. al. (J. Amer. Chem. Soc., 1979, 109, 4571), except that the methyl groups on the phenolic residues have been replaced by tert-butyl","abstract_html":"Three series of mixed-valence copper(II)-copper(I) complexes of macrocyclic ligands have been prepared to examine systematically the factors affecting intramolecular electron transfer. The mixed-valence complexes are similar to the one prepared by Gagne et. al. (J. Amer. Chem. Soc., 1979, 109, 4571), except that the methyl groups on the phenolic residues have been replaced by tert-butyl","abstract_has_math":false,"creators":["Long, Russell C."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2014,"date_issued":"2014-12-15T23:18:30Z","date_published":"2014-12-15T23:18:30Z","updated_at":"2026-07-22T22:26:02Z","subjects":["Chemistry, Inorganic"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(UMI)AAI8521821"],"render_values":[{"text":"(UMI)AAI8521821","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/70302","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Long, Russell C."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2014-12-15T23:18:30Z","10000-01-01","1985"]},{"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"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/70302","(UMI)AAI8521821"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Three series of mixed-valence copper(II)-copper(I) complexes of macrocyclic ligands have been prepared to examine systematically the factors affecting intramolecular electron transfer. The mixed-valence complexes are similar to the one prepared by Gagne et. al. (J. Amer. Chem. Soc., 1979, 109, 4571), except that the methyl groups on the phenolic residues have been replaced by tert-butyl","substituents. The diimine linkages were also varied in the series of complexes.","(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","The five complexes in the first series possess equivalent copper sites, where B = B' = propylene(I), 2,2'-dimethylpropylene(II), butylene(III), 2,2'-biphenylene(IV), 1,3-cyclohexylene(IX). The four complexes of the second group contain asymmetric copper sties, where B = propylene; B' = 2,2'-dimethylpropylene(V), 2,2'-biphenylene(VI), butylene(VII), 1,8-naphthalene(X). The three complexes of the third series contain electronic donor type groups, two alcohol complexes where B = B' = 2-hydroxypropylene(VIII), B = propylene; B' = 2-hydroxypropylene(XI), and complex(XII) where the diimine linkages of complex III have been chemically reduced to amine linkages. The complexes were prepared by reducing the parent dicopper(II) complexes with dithionite. Variable-temperature EPR data, taken for acetone solutions from 373 to 100 K, are presented. In the low-temperature glass medium, each complex exhibits an EPR localized spectrum. At ambient temperatures in solution, complexes I, II, III, V, VIII and XI are EPR delocalized, while complexes IV, VI, VII, IX, X and XII are EPR localized. The approximate temperature for the conversion in solution from EPR delocalized to EPR localized were gathered for the complexes delocalized at ambient temperatures. Electrochemical data, cyclic voltammograms and differential pulse voltammograms, and electronic absorption spectra, intervalence transfer (IT) bands and d-d bands are given for each complex. Magnetic data are reported for several of the dicopper(II) complexes.","Made available in DSpace on 2014-12-15T23:18:30Z (GMT). No. of bitstreams: 1 8521821.pdf: 5718381 bytes, checksum: 974b208bd9b03f5b47ba656e4419a651 (MD5) Previous issue date: 1985","Embargo set by: Seth Robbins for item 70468 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","244 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985."]},{"key":"dc:title","label":"Title","values":["Electron Transfer in a Series of Mixed-Valence Copper(ii)-Copper(i) Complexes (Epr, Electrochemistry, It Bands, Magnetism)"]}]}],"canonical_facts":{"dc:creator":["Long, Russell C."],"dc:date":["2014-12-15T23:18:30Z","10000-01-01","1985"],"dc:description":["Three series of mixed-valence copper(II)-copper(I) complexes of macrocyclic ligands have been prepared to examine systematically the factors affecting intramolecular electron transfer. The mixed-valence complexes are similar to the one prepared by Gagne et. al. (J. Amer. Chem. Soc., 1979, 109, 4571), except that the methyl groups on the phenolic residues have been replaced by tert-butyl","substituents. The diimine linkages were also varied in the series of complexes.","(DIAGRAM, TABLE OR GRAPHIC OMITTED...PLEASE SEE DAI)","The five complexes in the first series possess equivalent copper sites, where B = B' = propylene(I), 2,2'-dimethylpropylene(II), butylene(III), 2,2'-biphenylene(IV), 1,3-cyclohexylene(IX). The four complexes of the second group contain asymmetric copper sties, where B = propylene; B' = 2,2'-dimethylpropylene(V), 2,2'-biphenylene(VI), butylene(VII), 1,8-naphthalene(X). The three complexes of the third series contain electronic donor type groups, two alcohol complexes where B = B' = 2-hydroxypropylene(VIII), B = propylene; B' = 2-hydroxypropylene(XI), and complex(XII) where the diimine linkages of complex III have been chemically reduced to amine linkages. The complexes were prepared by reducing the parent dicopper(II) complexes with dithionite. Variable-temperature EPR data, taken for acetone solutions from 373 to 100 K, are presented. In the low-temperature glass medium, each complex exhibits an EPR localized spectrum. At ambient temperatures in solution, complexes I, II, III, V, VIII and XI are EPR delocalized, while complexes IV, VI, VII, IX, X and XII are EPR localized. The approximate temperature for the conversion in solution from EPR delocalized to EPR localized were gathered for the complexes delocalized at ambient temperatures. Electrochemical data, cyclic voltammograms and differential pulse voltammograms, and electronic absorption spectra, intervalence transfer (IT) bands and d-d bands are given for each complex. Magnetic data are reported for several of the dicopper(II) complexes.","Made available in DSpace on 2014-12-15T23:18:30Z (GMT). No. of bitstreams: 1 8521821.pdf: 5718381 bytes, checksum: 974b208bd9b03f5b47ba656e4419a651 (MD5) Previous issue date: 1985","Embargo set by: Seth Robbins for item 70468 Lift date: Forever Reason: Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","Restricted to the U of I community idenfinitely during batch ingest of legacy ETDs","U of I Only","244 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1985."],"dc:identifier":["http://hdl.handle.net/2142/70302","(UMI)AAI8521821"],"dc:subject":["Chemistry, Inorganic"],"dc:title":["Electron Transfer in a Series of Mixed-Valence Copper(ii)-Copper(i) Complexes (Epr, Electrochemistry, It Bands, Magnetism)"],"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":"2026-07-22T22:26:02Z"}