A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence
A Chirally Locked Bis-perylene Diimide Macrocycle: Consequences for Chiral Self-Assembly and Circularly Polarized Luminescence
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DOI：
10.1021/jacs.3c13191
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发表时间：
2024-02-14
影响因子：
15
通讯作者：
Barendt，Timothy A.
中科院分区：
文献类型：
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作者：
Penty，Samuel E.;Orton，Georgia R. F.;Barendt，Timothy A.
含手性有机染料的大环对于开发超分子圆极化发光材料具有重要价值，其中预组织的手性框架有利于引导π -π自组装并传递强而持久的CPL信号。在这里，苝二酰亚胺（PDI）是有机染料组分的绝佳选择，因为除了具有可调的光物理和自组装特性外，PDI核心的功能化产生了扭曲的手性π-体系，能够进行cpld。然而，构型稳定的PDI大环很少，而且那些能够超越二聚体进行π -π自组装的大环是前所未有的，这两者都有利于稳健的自组装chiroptic材料。在这项工作中，我们报道了第一个构型稳定的双pdi环（ΔG⧧> 155 kJ mol-1）。我们使用这种手性锁定的大环来揭示手性PDI自组装的新知识，并对所得单晶材料进行新的定量CPL成像。因此，我们发现1,7-二取代PDI的手性为设计H-， J-和伴随的H-和J型自组装材料提供了合理的途径，这是优化（chir）光学和电荷/能量输运性质的重要安排。事实上，我们发现CPL在我们的手性大环的单晶中被放大，通过首次使用cpll激光扫描共聚焦显微镜量化从这些材料发射的光圆偏振的程度。
Macrocycles containing chiral organic dyes are highly valuable for the development of supramolecular circularly polarized luminescent (CPL) materials, where a preorganized chiral framework is conducive to directing π–π self-assembly and delivering a strong and persistent CPL signal. Here, perylene diimides (PDIs) are an excellent choice for the organic dye component because, alongside their tunable photophysical and self-assembly properties, functionalization of the PDI’s core yields a twisted, chiral π-system, capable of CPL. However, configurationally stable PDI-based macrocycles are rare, and those that are also capable of π–π self-assembly beyond dimers are unprecedented, both of which are advantageous for robust self-assembled chiroptical materials. In this work, we report the first bay-connected bis-PDI macrocycle that is configurationally stable (ΔG⧧> 155 kJ mol–1). We use this chirally locked macrocycle to uncover new knowledge of chiral PDI self-assembly and to perform new quantitative CPL imaging of the resulting single-crystal materials. As such, we discover that the chirality of a 1,7-disubstituted PDI provides a rational route to designing H-, J- and concomitant H- and J-type self-assembled materials, important arrangements for optimizing (chir)optical and charge/energy transport properties. Indeed, we reveal that CPL is amplified in the single crystals of our chiral macrocycle by quantifying the degree of emitted light circular polarization from such materials for the first time using CPL-Laser Scanning Confocal Microscopy.