Penty Samuel E, Orton Georgia R F, Black Dominic J, Pal Robert, Zwijnenburg Martijn A, Barendt Timothy A
School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT, U.K.
Department of Chemistry, University of Durham, South Road, Durham DH1 3LE, U.K.
J Am Chem Soc. 2024 Feb 28;146(8):5470-5479. doi: 10.1021/jacs.3c13191. Epub 2024 Feb 14.
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 (Δ > 155 kJ mol). 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.
含有手性有机染料的大环化合物对于超分子圆偏振发光（CPL）材料的开发具有极高价值，其中预先构建的手性框架有助于引导π-π自组装并产生强烈且持久的CPL信号。在此，苝二亚胺（PDI）是有机染料组分的绝佳选择，因为除了其可调节的光物理和自组装性质外，PDI核心的功能化会产生一个扭曲的手性π体系，能够实现CPL。然而，构型稳定的基于PDI的大环化合物很少见，而且能够进行二聚体以上的π-π自组装的化合物更是前所未有的，这两者对于坚固的自组装手性光学材料都很有利。在这项工作中，我们报道了首个构型稳定（Δ>155 kJ/mol）的湾连接双PDI大环化合物。我们使用这种手性锁定的大环化合物来揭示手性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型、J型以及伴随的H型和J型自组装材料提供了一条合理途径，这些排列对于优化（手性）光学和电荷/能量传输性质很重要。实际上，我们首次使用CPL激光扫描共聚焦显微镜对这类材料发射光的圆偏振程度进行定量，从而揭示了我们的手性大环化合物单晶中的CPL得到了放大。
