{"title":"通过铜催化叠氮化物-炔环加成制备具有延伸垂链的立体规则垂链电活性聚合物","authors":"Alexander Schmitt, Qingpei Wan, Barry C. Thompson","doi":"10.1002/pol.20230294","DOIUrl":null,"url":null,"abstract":"<p>Recent work on non-conjugated pendant electroactive polymers (NCPEPs) has demonstrated significant impacts of structural parameters such as backbone stereoregularity and the spacer connecting the pendant to the backbone on properties, most notably on charge carrier mobilities. Tuning of the pendant group however has not been reported for stereoregular NCPEPs. Here we present a family of novel isotactic poly((carbazolyl-alkyl-triazolyl)methyl methacrylates) (PCzATMMAs) for which the effects of increasing the pendant group from carbazole to 3,6-bis(4-(2-ethylhexyl)thiophen-2-yl)-carbazole were investigated. Based on unsuccessful post-polymerization functionalization with this extended group via previously reported transesterification and thiol-ene methodologies, we report functionalization via copper-catalyzed azide-alkyne cycloaddition which was demonstrated to be highly effective. The effect of spacer length was also investigated for comparison with previously established effects with alkyl spacers. Within the family of PCzATMMAs, hole mobilities were found to increase with longer spacer length and with thermal annealing. The incorporation of an extended pendant with alkyl solubilizing chains was found to result in a lower hole mobility than the equivalent polymer with an unfunctionalized pendant group. Importantly, the copper catalyzed azide-alkyne cycloaddition proved to be an effective method of post-polymerization functionalization for stereoregular NCPEPs when extending beyond a simple carbazole pendant.</p>","PeriodicalId":199,"journal":{"name":"Journal of Polymer Science Part A: Polymer Chemistry","volume":"61 18","pages":"2181-2187"},"PeriodicalIF":2.7020,"publicationDate":"2023-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20230294","citationCount":"0","resultStr":"{\"title\":\"Stereoregular pendant electroactive polymers with extended pendants via post-polymerization copper catalyzed azide-alkyne cycloaddition\",\"authors\":\"Alexander Schmitt, Qingpei Wan, Barry C. Thompson\",\"doi\":\"10.1002/pol.20230294\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Recent work on non-conjugated pendant electroactive polymers (NCPEPs) has demonstrated significant impacts of structural parameters such as backbone stereoregularity and the spacer connecting the pendant to the backbone on properties, most notably on charge carrier mobilities. Tuning of the pendant group however has not been reported for stereoregular NCPEPs. Here we present a family of novel isotactic poly((carbazolyl-alkyl-triazolyl)methyl methacrylates) (PCzATMMAs) for which the effects of increasing the pendant group from carbazole to 3,6-bis(4-(2-ethylhexyl)thiophen-2-yl)-carbazole were investigated. Based on unsuccessful post-polymerization functionalization with this extended group via previously reported transesterification and thiol-ene methodologies, we report functionalization via copper-catalyzed azide-alkyne cycloaddition which was demonstrated to be highly effective. The effect of spacer length was also investigated for comparison with previously established effects with alkyl spacers. Within the family of PCzATMMAs, hole mobilities were found to increase with longer spacer length and with thermal annealing. The incorporation of an extended pendant with alkyl solubilizing chains was found to result in a lower hole mobility than the equivalent polymer with an unfunctionalized pendant group. Importantly, the copper catalyzed azide-alkyne cycloaddition proved to be an effective method of post-polymerization functionalization for stereoregular NCPEPs when extending beyond a simple carbazole pendant.</p>\",\"PeriodicalId\":199,\"journal\":{\"name\":\"Journal of Polymer Science Part A: Polymer Chemistry\",\"volume\":\"61 18\",\"pages\":\"2181-2187\"},\"PeriodicalIF\":2.7020,\"publicationDate\":\"2023-06-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/pol.20230294\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Polymer Science Part A: Polymer Chemistry\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/pol.20230294\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"Materials Science\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Polymer Science Part A: Polymer Chemistry","FirstCategoryId":"1","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/pol.20230294","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Materials Science","Score":null,"Total":0}
Stereoregular pendant electroactive polymers with extended pendants via post-polymerization copper catalyzed azide-alkyne cycloaddition
Recent work on non-conjugated pendant electroactive polymers (NCPEPs) has demonstrated significant impacts of structural parameters such as backbone stereoregularity and the spacer connecting the pendant to the backbone on properties, most notably on charge carrier mobilities. Tuning of the pendant group however has not been reported for stereoregular NCPEPs. Here we present a family of novel isotactic poly((carbazolyl-alkyl-triazolyl)methyl methacrylates) (PCzATMMAs) for which the effects of increasing the pendant group from carbazole to 3,6-bis(4-(2-ethylhexyl)thiophen-2-yl)-carbazole were investigated. Based on unsuccessful post-polymerization functionalization with this extended group via previously reported transesterification and thiol-ene methodologies, we report functionalization via copper-catalyzed azide-alkyne cycloaddition which was demonstrated to be highly effective. The effect of spacer length was also investigated for comparison with previously established effects with alkyl spacers. Within the family of PCzATMMAs, hole mobilities were found to increase with longer spacer length and with thermal annealing. The incorporation of an extended pendant with alkyl solubilizing chains was found to result in a lower hole mobility than the equivalent polymer with an unfunctionalized pendant group. Importantly, the copper catalyzed azide-alkyne cycloaddition proved to be an effective method of post-polymerization functionalization for stereoregular NCPEPs when extending beyond a simple carbazole pendant.
期刊介绍:
Part A: Polymer Chemistry is devoted to studies in fundamental organic polymer chemistry and physical organic chemistry. This includes all related topics (such as organic, bioorganic, bioinorganic and biological chemistry of monomers, polymers, oligomers and model compounds, inorganic and organometallic chemistry for catalysts, mechanistic studies, supramolecular chemistry aspects relevant to polymer...