期刊
CHEMISTRY OF MATERIALS
卷 24, 期 22, 页码 4459-4467出版社
AMER CHEMICAL SOC
DOI: 10.1021/cm302915h
关键词
self-assembly; poly(3-hexylthiophene); Grignard metathesis polymerization; DFT
资金
- TN-SCORE
- NSF-EPSCOR [EPS-1004083]
- ORNL LDRD Program [5388]
- Office of Science, U.S. Department of Energy
- Office Of The Director
- EPSCoR [1004083] Funding Source: National Science Foundation
The synthesis of well-defined, end-functional poly(3-hexylthiophene)s (P3HTs) by in situ quenching of the Grignard metathesis (GRIM) polymerization is complicated by the extreme tendency to favor difunctional products in all but a few cases. A facile one-pot method for preparing 2-pyridyl and 3-pyridyl P3HTs with high abundance of monofunctional products is established via an examination of the kinetics of the end-functionalization quenching reaction with lithium chloride complexes of 2- and 3-pyridyl Grignard reagents. Density functional theory calculations guide the selection of pyridine as the end group, which provides the capacity to ligate cadmium selenide (CdSe) nanocrystals and arrests aggregation upon thermal annealing when dispersed in a P3HT matrix. The relative abundances of various end-functional products, as ascertained by high-resolution matrix assisted laser desorption ionization time-of-flight mass spectrometry, can be altered through the use of 1-pentene as an additive: GRIM polymerizations quenched with 3-pyridyl and 2-pyridyl Grignard reagents show 5% and 18% abundances of difunctional, pyridyl-capped P3HTs, respectively, when 1-pentene is present at 1000:1 relative to the nickel catalyst. This represents a significant improvement compared to quenching with aryl Grignard reagents, where difunctional products predominate. The ability to manipulate end group compositions coupled with the propensity of pyridyl-functionalized P3HTs to ligate semiconductor quantum dots (SQDs) opens new possibilities for tuning the morphology of conjugated polymer/SQD blends.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据