Designing Amphiphilic Conjugated Polyelectrolytes for Self-Assembly into Straight-Chain Rod-like Micelles
Designing Amphiphilic Conjugated Polyelectrolytes for Self-Assembly into Straight-Chain Rod-like Micelles
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DOI：
10.1021/acs.macromol.2c02057
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发表时间：
2023-04
期刊：
影响因子：
5.5
通讯作者：
K. J. Winchell;Patrick Y. Yee;Yolanda L. Li;Alexander F. Simafranca;Julia Chang;Christian Beren;Xinyu Liu;Diego Garcia Vidales;Robert Thompson;Charlene Z. Salamat;Quynh M. Duong;Robert S. Jordan;B. J. Schwartz;W. Gelbart;Y. Rubin;S. Tolbert
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文献类型：
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作者：
K. J. Winchell;Patrick Y. Yee;Yolanda L. Li;Alexander F. Simafranca;Julia Chang;Christian Beren;Xinyu Liu;Diego Garcia Vidales;Robert Thompson;Charlene Z. Salamat;Quynh M. Duong;Robert S. Jordan;B. J. Schwartz;W. Gelbart;Y. Rubin;S. Tolbert
半导体聚合物是一类多功能材料，可用于许多（光）电子应用，包括有机光伏发电。然而，它们本质上是无序的，并且由于沿着共轭主链的聚合物链的弯曲和扭结以及晶界处的无序而导致导电性差。为了减少聚合物无序，我们开发了一种通过创建两亲性共轭聚电解质（CPE）来拉直聚合物链的方法，这些聚电解质在水中自组装成蠕虫状胶束。目前的工作完善了 CPE 自组装的设计规则。我们介绍了一种直链胶束形成聚合物的合成和表征，该聚合物是聚（环戊二噻吩-替代噻吩）（PCT）的衍生物，每个环戊二噻吩单元带有两个带铵基团。通过小角 X 射线散射 (SAXS) 和冷冻电子显微镜 (cryo-EM) 观察 PCT 溶液相自组装成胶束的过程，而详细的 SAXS 拟合可以表征胶束内相互作用和胶束间聚集。我们发现，由于其交替的环戊二噻吩和噻吩亚基之间缺乏空间位阻，PCT 显示出显着的链伸直，这增加了聚合物自组装成直棒状胶束的倾向。这项工作扩展了形成胶束的半导体聚合物的可用性，并指出可以进一步增强以获得基于圆柱形胶束的均匀纳米结构聚合物组件。
Semiconducting polymers are a versatile class of materials that are used in many (opto)electronic applications, including organic photovoltaics. However, they are inherently disordered and suffer from poor conductivities due to bends and kinks in the polymer chains along the conjugated backbone, as well as disorder at grain boundaries. In an effort to reduce polymer disorder, we developed a method to straighten polymer chains by creating amphiphilic conjugated polyelectrolytes (CPEs) that self-assemble in water into worm-like micelles. The present work refines our design rules for self-assembly of CPEs. We present the synthesis and characterization of a straight, micelle-forming polymer, a derivative of poly(cyclopentadithiophene-alt-thiophene) (PCT) bearing two ammoniumcharged groups per cyclopentadithiophene unit. Solution-phase self-assembly of PCT into micelles is observed by both smallangle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-EM), while detailed SAXS fitting allows for characterization of intra-micellar interactions and inter-micelle aggregation. We find that PCT displays significant chain straightening thanks to the lack of steric hindrance between its alternating cyclopentadithiophene and thiophene subunits, which increases the propensity for the polymer to self-assemble into straight rod-like micelles. This work extends the availability of micelle-forming semiconducting polymers and points to further enhancements that can be made to obtain homogeneous nanostructured polymer assemblies based on cylindrical micelles.