Semiconducting Eggs and Ladders: Understanding Exciton Landscape Formation in Aqueous π-Conjugated Inter-Polyelectrolyte Complexes,Macromolecules

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Semiconducting Eggs and Ladders: Understanding Exciton Landscape Formation in Aqueous π-Conjugated Inter-Polyelectrolyte Complexes
Macromolecules ( IF 5.1 ) Pub Date : 2020-03-30 , DOI: 10.1021/acs.macromol.0c00029
William R. Hollingsworth ₁ , Vanessa Williams ₁ , Alexander L. Ayzner ₁

Affiliation

Conjugated polymers display remarkable optoelectronic properties that emerge from the strong coupling between delocalized π-electrons, leading to highly mobile excited states. This is a very useful property from a light-harvesting perspective. We showed previously that a promising and environmentally attractive approach to formation of an ultrafast light-harvesting antenna is to use aqueous ionic assembly of oppositely charged conjugated polyelectrolytes (CPEs). However, to rationally design the excited-state transfer efficiency, the basic physical chemistry of inter-CPE assembly must be elucidated. We demonstrate that the delocalization of π-electrons and the orientation of ionic sidechains relative to the conjugation plane together dictate the complexation kinetics and thermodynamics, and thus the resulting structure. We find that the enthalpy of complexation is substantially larger than previously observed with nonconjugated polyelectrolytes. We further show that the reaction enthalpy changes sign with increasing temperature. We argue that the interaction between the water solvation shell and the polarizable aromatic backbone is key to understanding both the activation energy and the reaction enthalpy.

中文翻译：

半导体蛋和梯子：了解π共轭水间电解质复合物中激子的景观形成

共轭聚合物显示出非凡的光电性能，这是由离域π电子之间的强耦合产生的，从而导致了高度移动的激发态。从光收集的角度来看，这是一个非常有用的属性。先前我们已经证明，形成超快光捕获天线的一种有前途且对环境有吸引力的方法是使用带相反电荷的共轭聚电解质（CPE）的水性离子组件。但是，要合理设计激发态转移效率，必须阐明CPE间组装的基本物理化学。我们证明，π电子的离域和离子侧链相对于共轭平面的取向共同决定了络合动力学和热力学，从而决定了结构。我们发现络合焓显着大于以前用非共轭聚电解质观察到的焓。我们进一步表明，反应焓随温度升高而变化。我们认为，水溶剂化壳与可极化芳香族骨架之间的相互作用是理解活化能和反应焓的关键。

更新日期：2020-04-24

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