{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/21096"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/21096","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Porphyrin liquid crystals","abstract":"Made available in DSpace on 2011-05-07T12:58:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712399.pdf: 6112917 bytes, checksum: 8710d51cba58a5e941a2d63d6e735ca7 (MD5) Previous issue date: 1996","abstract_html":"Made available in DSpace on 2011-05-07T12:58:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712399.pdf: 6112917 bytes, checksum: 8710d51cba58a5e941a2d63d6e735ca7 (MD5) Previous issue date: 1996","abstract_has_math":false,"creators":["Patel, Bimal Ramesh"],"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":"2011-05-07T12:58:15Z","date_published":"2011-05-07T12:58:15Z","updated_at":"2026-07-22T22:25:17Z","subjects":["Chemistry, Inorganic","Chemistry, Organic","Engineering, Materials Science"],"languages":["eng"],"rights":["Copyright 1996 Patel, Bimal Ramesh"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591200140","AAI9712399","(UMI)AAI9712399"],"render_values":[{"text":"9780591200140","href":null,"code":true},{"text":"AAI9712399","href":null,"code":true},{"text":"(UMI)AAI9712399","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/21096","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":["Patel, Bimal Ramesh"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2011-05-07T12:58:15Z","10000-01-01","1996"]},{"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, Organic","Engineering, Materials Science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1996 Patel, Bimal Ramesh"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591200140","AAI9712399","(UMI)AAI9712399","http://hdl.handle.net/2142/21096"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Made available in DSpace on 2011-05-07T12:58:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712399.pdf: 6112917 bytes, checksum: 8710d51cba58a5e941a2d63d6e735ca7 (MD5) Previous issue date: 1996","\"A new family of tetraarylporphyrins has been synthesized. The key distinguishing feature of these porphyrins is the presence of carboxylic functionality at the eight meta-phenyl positions of tetraphenylporphyrin (TPP). The base porphyrin is called 5,10,15,20-tetrakis(3$\\sp\\prime,5\\sp\\prime$-dicarboxyphenyl)porphyrin (H$\\sb2$DCarPP). The octa-meta-phenyl substitution pattern allows substituents at the meta positions to direct out and away from the molecular center in three dimensions. These outward-directed alkyl groups created pockets above and below the porphine plane. The \"\"bis-pocket\"\" shape is the critical design feature that gives this family of porphyrins novel and exciting properties.\"","The synthesis and characterization of H$\\sb2$DCarPP, starting with mesitylene, is presented in Chapter 2. A benchtop process for oxidizing mesitylene to uvitic acid has been developed, and it is the key step to obtaining H$\\sb2$DCarPP on a gram scale. An unusual crystal structure of an octapyridine-H$\\sb2$DCarPP complex is also presented. This host-guest structure shows large, solvent-filled channels in one dimension, and porphyrin-pyridine-porphyrin layers in the other dimensions.","Octa-n-alkyl esters of H$\\sb2$DCarPP have also been prepared. The synthesis and characterization of these alkyl H$\\sb2$DCarPP derivatives are presented in Chapters 3 and 4. The C$\\sb{10}$ to C$\\sb{22}$ octa-n-alkyl esters are liquid crystals. In fact, the C$\\sb{10}$ and C$\\sb{12}$ derivatives are liquid crystalline at room temperature. The C$\\sb{10}$ derivative has a liquid crystalline temperature range from $-3\\sp\\circ$C to 120$\\sp\\circ$C, the largest range of the series. The bis-pocket shape of the $\\rm C\\sb{12}\\ H\\sb2$DCarPP allows it to retain its liquid crystalline properties when metalated with five-coordinate metal ions like the vanadyl ion (VO$\\sp{\\rm II}$). By comparison, $\\rm C\\sb{12}\\ H\\sb2$TCPP (5,10,15,20-tetrakis(p-carboxyphenyl)porphyrin), a relatively flat molecule, loses its liquid crystalline properties when it is metalated with the vanadyl ion.","The alkyl H$\\sb2$DCarPP liquid crystals were studied by polarized microscopy. A model for the structure of the liquid crystalline phase is developed from analysis of the birefringence textures of the homologous series of alkyl H$\\sb2$DCarPP liquid crystals. X-ray diffraction studies contribute additional information about the mesophase structure. The electron paramagnetic resonance of the C$\\sb{12}$ DCarPPVO complex at room temperature gives a broad isotropic signal with lack of hyperfine structure.","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:48:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:21:56-05:00 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":["Porphyrin liquid crystals"]}]}],"canonical_facts":{"dc:contributor":["Kenneth S. Suslick"],"dc:creator":["Patel, Bimal Ramesh"],"dc:date":["2011-05-07T12:58:15Z","10000-01-01","1996"],"dc:description":["Made available in DSpace on 2011-05-07T12:58:15Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9712399.pdf: 6112917 bytes, checksum: 8710d51cba58a5e941a2d63d6e735ca7 (MD5) Previous issue date: 1996","\"A new family of tetraarylporphyrins has been synthesized. The key distinguishing feature of these porphyrins is the presence of carboxylic functionality at the eight meta-phenyl positions of tetraphenylporphyrin (TPP). The base porphyrin is called 5,10,15,20-tetrakis(3$\\sp\\prime,5\\sp\\prime$-dicarboxyphenyl)porphyrin (H$\\sb2$DCarPP). The octa-meta-phenyl substitution pattern allows substituents at the meta positions to direct out and away from the molecular center in three dimensions. These outward-directed alkyl groups created pockets above and below the porphine plane. The \"\"bis-pocket\"\" shape is the critical design feature that gives this family of porphyrins novel and exciting properties.\"","The synthesis and characterization of H$\\sb2$DCarPP, starting with mesitylene, is presented in Chapter 2. A benchtop process for oxidizing mesitylene to uvitic acid has been developed, and it is the key step to obtaining H$\\sb2$DCarPP on a gram scale. An unusual crystal structure of an octapyridine-H$\\sb2$DCarPP complex is also presented. This host-guest structure shows large, solvent-filled channels in one dimension, and porphyrin-pyridine-porphyrin layers in the other dimensions.","Octa-n-alkyl esters of H$\\sb2$DCarPP have also been prepared. The synthesis and characterization of these alkyl H$\\sb2$DCarPP derivatives are presented in Chapters 3 and 4. The C$\\sb{10}$ to C$\\sb{22}$ octa-n-alkyl esters are liquid crystals. In fact, the C$\\sb{10}$ and C$\\sb{12}$ derivatives are liquid crystalline at room temperature. The C$\\sb{10}$ derivative has a liquid crystalline temperature range from $-3\\sp\\circ$C to 120$\\sp\\circ$C, the largest range of the series. The bis-pocket shape of the $\\rm C\\sb{12}\\ H\\sb2$DCarPP allows it to retain its liquid crystalline properties when metalated with five-coordinate metal ions like the vanadyl ion (VO$\\sp{\\rm II}$). By comparison, $\\rm C\\sb{12}\\ H\\sb2$TCPP (5,10,15,20-tetrakis(p-carboxyphenyl)porphyrin), a relatively flat molecule, loses its liquid crystalline properties when it is metalated with the vanadyl ion.","The alkyl H$\\sb2$DCarPP liquid crystals were studied by polarized microscopy. A model for the structure of the liquid crystalline phase is developed from analysis of the birefringence textures of the homologous series of alkyl H$\\sb2$DCarPP liquid crystals. X-ray diffraction studies contribute additional information about the mesophase structure. The electron paramagnetic resonance of the C$\\sb{12}$ DCarPPVO complex at room temperature gives a broad isotropic signal with lack of hyperfine structure.","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T14:48:27Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:21:56-05:00 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":["9780591200140","AAI9712399","(UMI)AAI9712399","http://hdl.handle.net/2142/21096"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Patel, Bimal Ramesh"],"dc:subject":["Chemistry, Inorganic","Chemistry, Organic","Engineering, Materials Science"],"dc:title":["Porphyrin liquid crystals"],"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":"2026-07-22T22:25:17Z"}