How to reprogram the excitonic properties and solid-state morphologies of π-conjugated supramolecular polymers,Physical Chemistry Chemical Physics

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How to reprogram the excitonic properties and solid-state morphologies of π-conjugated supramolecular polymers
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2020-12-11 , DOI: 10.1039/d0cp04819d
Kaixuan Liu _{1,

2,

3} , Victor Paulino _{1,

2,

3} , Arindam Mukhopadhyay _{1,

2,

3} , Brianna Bernard _{1,

2,

3} , Amar Kumbhar _{3,

4,

5} , Chuan Liu _{1,

2,

3} , Jean-Hubert Olivier _{1,

2,

3}

Affiliation

The development of supramolecular tools to modulate the excitonic properties of non-covalent assemblies paves the way to engineer new classes of semicondcuting materials relevant to flexible electronics. While controlling the assembly pathways of organic chromophores enables the formation of J-like and H-like aggregates, strategies to tailor the excitonic properties of pre-assembled aggregates through post-modification are scarce. In the present contribution, we combine supramolecular chemistry with redox chemistry to modulate the excitonic properties and solid-state morphologies of aggregates built from stacks of water-soluble perylene diimide building blocks. The n-doping of initially formed aggregates in an aqueous medium is shown to produce π–anion stacks for which spectroscopic properties unveil a non-negligible degree of electron–electron interactions. Oxidation of the n-doped intermediates produces metastable aggregates where free exciton bandwidths (Ex_BW) increase as a function of time. Kinetic data analysis reveals that the dynamic increase of free exciton bandwidth is associated with the formation of superstructures constructed by means of a nucleation-growth mechanism. By designing different redox-assisted assembly pathways, we highlight that the sacrificial electron donor plays a non-innocent role in regulating the structure–function properties of the final superstructures. Furthermore, supramolecular architectures formed via a nucleation-growth mechanism evolve into ribbon-like and fiber-like materials in the solid-state, as characterized by SEM and HRTEM. Through a combination of ground-state electronic absorption spectroscopy, electrochemistry, spectroelectrochemistry, microscopy, and modeling, we show that redox-assisted assembly provides a means to reprogram the structure–function properties of pre-assembled aggregates.

中文翻译：

如何重新编程π共轭超分子聚合物的激子性质和固态形态

用于调节非共价组件的激子特性的超分子工具的开发为工程设计与柔性电子学相关的新型半导电材料铺平了道路。虽然控制有机发色团的组装途径能够形成J型和H型聚集体，但缺乏通过后修饰修饰预组装聚集体的激子性质的策略。在目前的贡献中，我们将超分子化学与氧化还原化学相结合，以调节由水溶性per二酰亚胺构件构建而成的聚集体的激子性质和固态形态。在水介质中对最初形成的聚集体进行n掺杂可产生π阴离子叠层，其光谱性质揭示了不可忽略的电子-电子相互作用程度。n掺杂中间体的氧化产生亚稳态聚集体，其中自由激子带宽（例如_BW）随时间增加。动力学数据分析表明，自由激子带宽的动态增加与通过成核-生长机制构造的超结构的形成有关。通过设计不同的氧化还原辅助组装途径，我们强调了牺牲电子给体在调节最终超结构的结构-功能特性中起着非无害的作用。此外，超分子结构通过通过SEM和HRTEM表征，成核生长机理演变成固态的带状和纤维状材料。通过结合基态电子吸收光谱，电化学，光谱电化学，显微镜和建模，我们表明氧化还原辅助组装提供了一种重新编程预组装聚集体的结构-功能特性的方法。

更新日期：2021-01-25

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