Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872, USA.
School of Fundamental Sciences, China Medical University, Shenyang 110122, China.
Molecules. 2017 Sep 18;22(9):1564. doi: 10.3390/molecules22091564.
A synthetic method that taps into the facile Lewis base (LB)→Lewis acid (LA) adduct forming reaction between the semiconducting polymeric LB and all carbon LA C for the construction of covalently linked donor-acceptor dyads and brush polymer of dyads is reported. The polymeric LB is built on poly(3-hexylthiophene) (P3HT) macromers containing either an alkyl or vinyl imidazolium end group that can be readily converted into the -heterocyclic carbene (NHC) LB site, while the brush polymer architecture is conveniently constructed via radical polymerization of the macromer P3HT with the vinyl imidazolium chain end. Simply mixing of such donor polymeric LB with C rapidly creates linked P3HT-C dyads and brush polymer of dyads in which C is covalently linked to the NHC junction connecting the vinyl polymer main chain and the brush P3HT side chains. Thermal behaviors, electronic absorption and emission properties of the resulting P3HT-C dyads and brush polymer of dyads have been investigated. The results show that a change of the topology of the P3HT-C dyad from linear to brush architecture enhances the crystallinity and of the P3HT domain and, along with other findings, they indicate that the brush polymer architecture of donor-acceptor domains provides a promising approach to improve performances of polymer-based solar cells.
报道了一种利用半导体聚合物 LB 与全碳 LA C 之间的易形成路易斯碱（LB）→路易斯酸（LA）加合物的合成方法，用于构建共价连接给体-受体二聚体和二聚体刷状聚合物。聚合物 LB 构建在含有烷基或乙烯基咪唑鎓端基的聚（3-己基噻吩）（P3HT）大分子单体上，这些端基可以很容易转化为 -杂环卡宾（NHC）LB 位点，而刷状聚合物结构则可以通过大分子单体 P3HT 与乙烯基咪唑鎓链末端的自由基聚合方便地构建。只需将这种供体聚合物 LB 与 C 混合，就可以快速生成连接的 P3HT-C 二聚体和刷状聚合物的二聚体，其中 C 通过连接乙烯基聚合物主链和刷状 P3HT 侧链的 NHC 连接点与 P3HT 共价连接。对所得 P3HT-C 二聚体和刷状聚合物的二聚体的热行为、电子吸收和发射性质进行了研究。结果表明，P3HT-C 二聚体的拓扑结构从线性到刷状结构的变化增强了 P3HT 区域的结晶度和 ，并且结合其他发现，它们表明给体-受体结构域的刷状聚合物结构为改善基于聚合物的太阳能电池的性能提供了一种很有前途的方法。
