Stereoregular pendant electroactive polymers with extended pendants via post‐polymerization copper catalyzed azide‐alkyne cycloaddition
Stereoregular pendant electroactive polymers with extended pendants via post‐polymerization copper catalyzed azide‐alkyne cycloaddition
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DOI：
10.1002/pol.20230294
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发表时间：
2023-06
影响因子：
3.4
通讯作者：
Alexander Schmitt;Qing-Xia Wan;B. Thompson
中科院分区：
文献类型：
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作者：
Alexander Schmitt;Qing-Xia Wan;B. Thompson
最近对非共轭侧基电活性聚合物（NCPEP）的研究表明，结构参数（如主链立构规整性和连接侧基与主链的间隔基）对性质，尤其是对电荷载流子迁移率有显著影响。然而，对于有规立构的NCPEP，尚未报道侧基的调谐。在这里，我们提出了一个家庭的新的全同立构聚（（咔唑基-烷基-三唑基）甲基丙烯酸甲酯）（PCzATMMA），其中增加侧基从咔唑到3，6-双（4-（2-乙基己基）噻吩-2-基）-咔唑的影响进行了研究。基于通过先前报道的酯交换和硫醇-烯方法用该扩展基团进行的不成功的聚合后官能化，我们报道了通过铜催化的叠氮-炔环加成进行的官能化，这被证明是非常有效的。间隔长度的影响也进行了研究，与以前建立的烷基间隔的影响进行比较。在家庭的PCzATMMA，空穴迁移率被发现增加较长的间隔长度和热退火。发现具有烷基增溶链的延伸侧基的掺入导致比具有未官能化侧基的等效聚合物更低的空穴迁移率。重要的是，铜催化的叠氮-炔环加成被证明是一种有效的方法，后聚合官能化的立构规整NCPEP时，超出了简单的咔唑侧。
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.