{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/84215"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/84215","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Solid Phase Synthesis of M-Phenylene Ethynylene Oligomer Heterosequences","abstract":"The synthesis of m-phenylene ethynylene (mPE) oligomers is currently a tedious process. To address this, two methods for the solid-phase synthesis of mPE oligomers (including heterosequences) have been developed. The first strategy employs a silyl-acetylene linker attached to ArgoGel(TM) solid support, and uses palladium-catalyzed cross-coupling reactions to form the desired mPE backbone in a monomer-by-monomer fashion. In order to rapidly access hexameric oligomers in a period of one to two days, efforts were taken to limit the need for deprotection steps and ensure cross-coupling conditions were complete within two hours. This led to the ability to produce mPE heterosequence hexamers with aryl bromide and terminal acetylene endgroups in good yields (typically 55-75%), in twelve hours. To increase the diversity of mPE oligomer endgroups available from solid-phase methods, a new strategy based on a triazene linker and Merrifield resin was also investigated. In this approach the mPE backbone was constructed in the same fashion as used in the silyl-acetylene linker approach. However, due to differences in resin swelling, some modification of reaction conditions were required. These new conditions allowed mPE heterosequences with aryl iodide and TMS-acetylene endgroups to be produced in 45-65% yields in forty-eight hours. Both solid-phase methods were able to produce oligomers of up to nine or ten repeat units. A method for obtaining longer-length oligomers was, however, necessary. To achieve this, a method of on-resin fragment coupling was investigated. This strategy employed previously established synthetic conditions to couple oligomer fragments onto a solid support through a silyl-acetylene linker. The on-resin mPE fragments were then subjected to a sequence of deprotection and coupling steps in order to access the desired length mPE oligomers in low, but acceptable yields. Aggregation of resin-bound oligomers may be attributed to the lack of conversion observed for the room temperature on-resin fragment coupling. Disruption of on-resin aggregates was achieved by elevating the temperature of coupling reactions.","abstract_html":"The synthesis of m-phenylene ethynylene (mPE) oligomers is currently a tedious process. To address this, two methods for the solid-phase synthesis of mPE oligomers (including heterosequences) have been developed. The first strategy employs a silyl-acetylene linker attached to ArgoGel(TM) solid support, and uses palladium-catalyzed cross-coupling reactions to form the desired mPE backbone in a monomer-by-monomer fashion. In order to rapidly access hexameric oligomers in a period of one to two days, efforts were taken to limit the need for deprotection steps and ensure cross-coupling conditions were complete within two hours. This led to the ability to produce mPE heterosequence hexamers with aryl bromide and terminal acetylene endgroups in good yields (typically 55-75%), in twelve hours. To increase the diversity of mPE oligomer endgroups available from solid-phase methods, a new strategy based on a triazene linker and Merrifield resin was also investigated. In this approach the mPE backbone was constructed in the same fashion as used in the silyl-acetylene linker approach. However, due to differences in resin swelling, some modification of reaction conditions were required. These new conditions allowed mPE heterosequences with aryl iodide and TMS-acetylene endgroups to be produced in 45-65% yields in forty-eight hours. Both solid-phase methods were able to produce oligomers of up to nine or ten repeat units. A method for obtaining longer-length oligomers was, however, necessary. To achieve this, a method of on-resin fragment coupling was investigated. This strategy employed previously established synthetic conditions to couple oligomer fragments onto a solid support through a silyl-acetylene linker. The on-resin mPE fragments were then subjected to a sequence of deprotection and coupling steps in order to access the desired length mPE oligomers in low, but acceptable yields. Aggregation of resin-bound oligomers may be attributed to the lack of conversion observed for the room temperature on-resin fragment coupling. Disruption of on-resin aggregates was achieved by elevating the temperature of coupling reactions.","abstract_has_math":false,"creators":["Ray, Christian R."],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Moore, Jeffrey S."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2015,"date_issued":"2015-09-25T22:13:31Z","date_published":"2015-09-25T22:13:31Z","updated_at":"2026-07-22T22:26:22Z","subjects":["Chemistry, Polymer"],"languages":["eng"],"rights":[],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["(MiAaPQ)AAI3202158"],"render_values":[{"text":"(MiAaPQ)AAI3202158","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/84215","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Moore, Jeffrey S."]},{"key":"dc:creator","label":"Author","values":["Ray, Christian R."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2015-09-25T22:13:31Z","10000-01-01","2005"]},{"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, Polymer"]}]},{"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/2142/84215","(MiAaPQ)AAI3202158"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["The synthesis of m-phenylene ethynylene (mPE) oligomers is currently a tedious process. To address this, two methods for the solid-phase synthesis of mPE oligomers (including heterosequences) have been developed. The first strategy employs a silyl-acetylene linker attached to ArgoGel(TM) solid support, and uses palladium-catalyzed cross-coupling reactions to form the desired mPE backbone in a monomer-by-monomer fashion. In order to rapidly access hexameric oligomers in a period of one to two days, efforts were taken to limit the need for deprotection steps and ensure cross-coupling conditions were complete within two hours. This led to the ability to produce mPE heterosequence hexamers with aryl bromide and terminal acetylene endgroups in good yields (typically 55-75%), in twelve hours. To increase the diversity of mPE oligomer endgroups available from solid-phase methods, a new strategy based on a triazene linker and Merrifield resin was also investigated. In this approach the mPE backbone was constructed in the same fashion as used in the silyl-acetylene linker approach. However, due to differences in resin swelling, some modification of reaction conditions were required. These new conditions allowed mPE heterosequences with aryl iodide and TMS-acetylene endgroups to be produced in 45-65% yields in forty-eight hours. Both solid-phase methods were able to produce oligomers of up to nine or ten repeat units. A method for obtaining longer-length oligomers was, however, necessary. To achieve this, a method of on-resin fragment coupling was investigated. This strategy employed previously established synthetic conditions to couple oligomer fragments onto a solid support through a silyl-acetylene linker. The on-resin mPE fragments were then subjected to a sequence of deprotection and coupling steps in order to access the desired length mPE oligomers in low, but acceptable yields. Aggregation of resin-bound oligomers may be attributed to the lack of conversion observed for the room temperature on-resin fragment coupling. Disruption of on-resin aggregates was achieved by elevating the temperature of coupling reactions.","Made available in DSpace on 2015-09-25T22:13:31Z (GMT). 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To address this, two methods for the solid-phase synthesis of mPE oligomers (including heterosequences) have been developed. The first strategy employs a silyl-acetylene linker attached to ArgoGel(TM) solid support, and uses palladium-catalyzed cross-coupling reactions to form the desired mPE backbone in a monomer-by-monomer fashion. In order to rapidly access hexameric oligomers in a period of one to two days, efforts were taken to limit the need for deprotection steps and ensure cross-coupling conditions were complete within two hours. This led to the ability to produce mPE heterosequence hexamers with aryl bromide and terminal acetylene endgroups in good yields (typically 55-75%), in twelve hours. To increase the diversity of mPE oligomer endgroups available from solid-phase methods, a new strategy based on a triazene linker and Merrifield resin was also investigated. In this approach the mPE backbone was constructed in the same fashion as used in the silyl-acetylene linker approach. However, due to differences in resin swelling, some modification of reaction conditions were required. These new conditions allowed mPE heterosequences with aryl iodide and TMS-acetylene endgroups to be produced in 45-65% yields in forty-eight hours. Both solid-phase methods were able to produce oligomers of up to nine or ten repeat units. A method for obtaining longer-length oligomers was, however, necessary. To achieve this, a method of on-resin fragment coupling was investigated. This strategy employed previously established synthetic conditions to couple oligomer fragments onto a solid support through a silyl-acetylene linker. The on-resin mPE fragments were then subjected to a sequence of deprotection and coupling steps in order to access the desired length mPE oligomers in low, but acceptable yields. Aggregation of resin-bound oligomers may be attributed to the lack of conversion observed for the room temperature on-resin fragment coupling. Disruption of on-resin aggregates was achieved by elevating the temperature of coupling reactions.","Made available in DSpace on 2015-09-25T22:13:31Z (GMT). No. of bitstreams: 2 license.txt: 4848 bytes, checksum: 96035ab3f5e1c23cc7138a224ce498bd (MD5) 3202158.pdf: 4664435 bytes, checksum: a67250909750a96b662ee6e4993f400b (MD5) Previous issue date: 2005","Embargo set by: Seth Robbins for item 85496 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","158 p.","Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2005."],"dc:identifier":["http://hdl.handle.net/2142/84215","(MiAaPQ)AAI3202158"],"dc:language":["eng"],"dc:subject":["Chemistry, Polymer"],"dc:title":["Solid Phase Synthesis of M-Phenylene Ethynylene Oligomer Heterosequences"],"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":"2026-07-22T22:26:22Z"}