Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust light-harvesting nanoscale objects
Covalent post-assembly modification of π-conjugated supramolecular polymers delivers structurally robust light-harvesting nanoscale objects
复制标题
α-共轭超分子聚合物的共价后组装修饰可提供结构坚固的光捕获纳米级物体
DOI：
10.1039/d2nr06806k
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发表时间：
2023
期刊：
影响因子：
6.7
通讯作者：
Olivier, Jean-Hubert
中科院分区：
文献类型：
--
作者：
Paulino, Victor;Liu, Kaixuan;Cesiliano, Valentino;Tsironi, Ifigeneia;Mukhopadhyay, Arindam;Kaufman, Maria;Olivier, Jean-Hubert
一个双组分钉合策略是用来共价拴一类新的水溶性超分子聚合物从海湾功能化的？通过利用激子耦合和荧光数据被利用作为光谱报告的一种新的组合策略，建立了结构设计原则，以形成其基态电子性质对溶剂化环境不敏感的捕光超结构。此外，我们通过利用荧光量子产率对母体超分子组装体的急剧变化来询问钉扎超结构的结构性质。从本质上讲，我们的工作表明，激子耦合测量和光致发光实验的结合描绘了一个更准确的理解所需的设计原则，以限制结构缺陷的程度，并放大在这类新的溶剂化纳米级物体的氧化还原活性单元之间的短程和长程电子耦合。这些结果表明，非共价组装，这是由弱的二级相互作用调节的脆弱的构象，可以保存通过组装后的预成型的超分子聚合物的改性。这些合成和光谱原理可以反过来被编入实验手柄，以参数化光捕获纳米级物体的光电特性。
A two-component stapling strategy is used to covalently tether a new class of water-soluble supramolecular polymers built from bay-functionalized perylene bisimide (PBI) units. By leveraging a novel combined strategy where excitonic coupling and fluorescence data are exploited as spectroscopic reporters, structural design principles are established to form light-harvesting superstructures whose ground-state electronic properties are not sensitive to solvation environments. Moreover, we interrogate the structural properties of stapled superstructures by capitalizing on the drastic changes in fluorescence quantum yields against parent supramolecular assemblies. In essence, our work shows that the combination of excitonic coupling measurements and photoluminescence experiments delineates a more accurate understanding of the design principles required to limit the degree of structural defects and magnify short- and long-range electronic couplings between redox-active units in this new class of solvated nanoscale objects. These results highlight that the fragile conformation of non-covalent assemblies, which are regulated by weak secondary interactions, can be preserved by post-assembly modification of preformed supramolecular polymers. These synthetic and spectroscopic principles can in turn be codified as experimental handles to parameterize the optoelectronic properties of light-harvesting nanoscale objects.