{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84402"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84402","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Structural Studies of Penetrated Ion Pairs Using Chiral Cyanine Borates","abstract":"An induced circular dichroism (CD) spectrum is observed for 1,1$\\sp\\prime,3,3,3\\sp\\prime,3\\sp\\prime$-hexamethyl-9-phenyl-indo-carbocyanine, 1,1$\\sp\\prime$-diethyl-2,2$\\sp\\prime$-cyanine, 1,1$\\sp\\prime$-di-(3,5-di-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine, or 1,1$\\sp\\prime$-di-(4-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine when penetrated into a chiral cavity of either spirobi- ((2-methyl)borataxanthene) or spirobi- ((3-methyl)borataxanthene). Within the ion pair, the cyanine dye exists in two (or more) interconverting conformations of unequal energy. Solid state structural evidence suggests that a nitrogen-forward mode for penetration by the cyanine dominates the solution behavior. A critical feature for the detection of the induced circular dichroism spectrum is that the dye is twisted in the ground state. The free energy difference between the diastereomers with right- and left-handed twist in the chiral cavity of the borate is less than 1 kcal/mol, but this is sufficient to induce the CD spectrum. The magnitude of observed CD spectrum is dependent on the structure of both the cyanine and borate.","abstract_html":"An induced circular dichroism (CD) spectrum is observed for 1,1$\\sp\\prime,3,3,3\\sp\\prime,3\\sp\\prime$-hexamethyl-9-phenyl-indo-carbocyanine, 1,1$\\sp\\prime$-diethyl-2,2$\\sp\\prime$-cyanine, 1,1$\\sp\\prime$-di-(3,5-di-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine, or 1,1$\\sp\\prime$-di-(4-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine when penetrated into a chiral cavity of either spirobi- ((2-methyl)borataxanthene) or spirobi- ((3-methyl)borataxanthene). Within the ion pair, the cyanine dye exists in two (or more) interconverting conformations of unequal energy. Solid state structural evidence suggests that a nitrogen-forward mode for penetration by the cyanine dominates the solution behavior. A critical feature for the detection of the induced circular dichroism spectrum is that the dye is twisted in the ground state. The free energy difference between the diastereomers with right- and left-handed twist in the chiral cavity of the borate is less than 1 kcal/mol, but this is sufficient to induce the CD spectrum. The magnitude of observed CD spectrum is dependent on the structure of both the cyanine and borate.","abstract_has_math":true,"creators":["Owen, David John"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Schuster, Gary B."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:14:18Z","date_published":"2015-09-25T22:14:18Z","updated_at":"2026-07-22T22:26:23Z","subjects":["Chemistry, Organic"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI9834726"],"render_values":[{"text":"(MiAaPQ)AAI9834726","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84402","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Schuster, Gary B."]},{"key":"dc:creator","label":"Author","values":["Owen, David John"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:14:18Z","10000-01-01","1998"]},{"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, Organic"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/2142/84402","(MiAaPQ)AAI9834726"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["An induced circular dichroism (CD) spectrum is observed for 1,1$\\sp\\prime,3,3,3\\sp\\prime,3\\sp\\prime$-hexamethyl-9-phenyl-indo-carbocyanine, 1,1$\\sp\\prime$-diethyl-2,2$\\sp\\prime$-cyanine, 1,1$\\sp\\prime$-di-(3,5-di-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine, or 1,1$\\sp\\prime$-di-(4-tert-butyl)benzyl-2,2$\\sp\\prime$-cyanine when penetrated into a chiral cavity of either spirobi- ((2-methyl)borataxanthene) or spirobi- ((3-methyl)borataxanthene). Within the ion pair, the cyanine dye exists in two (or more) interconverting conformations of unequal energy. Solid state structural evidence suggests that a nitrogen-forward mode for penetration by the cyanine dominates the solution behavior. A critical feature for the detection of the induced circular dichroism spectrum is that the dye is twisted in the ground state. The free energy difference between the diastereomers with right- and left-handed twist in the chiral cavity of the borate is less than 1 kcal/mol, but this is sufficient to induce the CD spectrum. The magnitude of observed CD spectrum is dependent on the structure of both the cyanine and borate.","Made available in DSpace on 2015-09-25T22:14:18Z (GMT). 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Within the ion pair, the cyanine dye exists in two (or more) interconverting conformations of unequal energy. Solid state structural evidence suggests that a nitrogen-forward mode for penetration by the cyanine dominates the solution behavior. A critical feature for the detection of the induced circular dichroism spectrum is that the dye is twisted in the ground state. The free energy difference between the diastereomers with right- and left-handed twist in the chiral cavity of the borate is less than 1 kcal/mol, but this is sufficient to induce the CD spectrum. The magnitude of observed CD spectrum is dependent on the structure of both the cyanine and borate.","Made available in DSpace on 2015-09-25T22:14:18Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 9834726.pdf: 4823130 bytes, checksum: 9b7cc85790f65c8e10b34bc5e16979a9 (MD5) Previous issue date: 1998","Embargo set by: Seth Robbins for item 85683 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","91 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1998."],"dc:identifier":["http://hdl.handle.net/2142/84402","(MiAaPQ)AAI9834726"],"dc:language":["eng"],"dc:subject":["Chemistry, Organic"],"dc:title":["Structural Studies of Penetrated Ion Pairs Using Chiral Cyanine Borates"],"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":"2026-07-22T22:26:23Z"}