{"id":{"repo_id":"columbia-diss","oai_identifier":"oai:academiccommons.columbia.edu:10.7916/D8TQ67X0"},"canonical_url":"https://search.dev.ndltd.org/etd/columbia-diss/oai:academiccommons.columbia.edu:10.7916/D8TQ67X0","repository":{"repo_id":"columbia-diss","name":"Columbia University","base_url":"https://academiccommons.columbia.edu/oai"},"display":{"title":"In pursuit of conjugation in one-dimension: Synthetic studies of oligomeric and polymeric organic materials","abstract":"Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases. Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior. Chapter 3. Functionaliztion of Diphenyloligoenes Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide.","abstract_html":"Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases. Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior. Chapter 3. Functionaliztion of Diphenyloligoenes Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide.","abstract_has_math":false,"creators":["Sedbrook, Danielle F."],"institution":null,"degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":[],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013","date_published":"2013","updated_at":"2026-07-24T01:44:34Z","subjects":["Chemistry","Oligomers","Polymers","Organic compounds--Synthesis"],"languages":["English"],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://doi.org/10.7916/D8TQ67X0","outbound_label":"DOI","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:creator","label":"Author","values":["Sedbrook, Danielle F."]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013"]},{"key":"dc:type","label":"Dc Type","values":["Theses"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Oligomers","Polymers","Organic compounds--Synthesis"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://doi.org/10.7916/D8TQ67X0"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases. Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior. Chapter 3. Functionaliztion of Diphenyloligoenes Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide."]},{"key":"dc:title","label":"Title","values":["In pursuit of conjugation in one-dimension: Synthetic studies of oligomeric and polymeric organic materials"]}]}],"canonical_facts":{"dc:creator":["Sedbrook, Danielle F."],"dc:date":["2013"],"dc:description":["Chapter 1. Ring-Opening Alkyne Metathesis Polymerization of Dibenzocyclooctynes A molybdenum(VI) propylidyne substituted with bidentate phenoxides will react with dibenzocyclooctynes in living ring-opening alkyne metathesis polymerization (ROAMP). The corresponding monodentate phenoxides do not yield well-controlled polymerizations. However, if the substrate in the ROAMP reaction is an aliphatic cyclooctyne, uncontrolled, non-living polymerizations take place in all cases. Chapter 2. Ring-Opening Alkyne Metathesis via a Tungstenatetrahedrane Intermediate A cyclopropenone-modified dibenzocyclooctyne will undergo a single ring opening alkyne metathesis reaction in the presence of Schrock's tris(tert-butoxy)tungsten(VI) neopentylidyne--a highly active alkyne metathesis catalyst. Despite the enormous amount of ring strain present in and related diphenycyclooctadiynes, these compounds do not readily undergo ring-opening alkyne metathesis polymerization (ROAMP), even with the most active alkyne metathesis catalysts available. The ring-opening of 1 proceeds via a tungstenatetrahedrane intermediate. Because of its sluggish reactivity, we were able to follow the ring-opening reaction by NMR to gain mechanistic insight into this remarkable behavior. Chapter 3. Functionaliztion of Diphenyloligoenes Bromine and carboxylic acid substituted α,ω-diphenyl-µ,ν-dicyano-oligoenes (DPDCn) were synthesized up to 9 and 7 olefin units in length, respectively. The carboxylic acid functionalized oligoenes (DPDCn-CO2H) are aligned through hydrogen bonding to DMF in the solid state. These can also be used to direct monolayer formation of Fe3O4 on single crystalline, 100 Gallium Arsenide."],"dc:identifier":["https://doi.org/10.7916/D8TQ67X0"],"dc:language":["English"],"dc:subject":["Chemistry","Oligomers","Polymers","Organic compounds--Synthesis"],"dc:title":["In pursuit of conjugation in one-dimension: Synthetic studies of oligomeric and polymeric organic materials"],"dc:type":["Theses"]},"updated_at":"2026-07-24T01:44:34Z"}