π-扩展吲哚吲哚利嗪的设计、合成和光电特性。

Przemysław, Gaweł, Abhishek, Pareek, Muhammad Yasir , Mehboob, Maciej, Majdecki, Hubert, Szabat, Piotr, Połczyński, Cina, Foroutan-Nejad, Maja, Morawiak
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摘要

开发稳定、可调的多环芳烃化合物(PACs)对于推动有机光电子学的发展至关重要。传统的多环芳烃(PAHs),例如烯类,往往由于光氧化和低聚作用而导致稳定性差,这与其前沿分子轨道能级有关。为了解决这些局限性,我们通过将吲哚和吲嗪分子合并到一个单一的多环框架中,设计并合成了一类新的π-扩展吲哚吲嗪类化合物。根据格莱德韦尔-劳埃德(Glidewell-Lloyd)规则的预测,在融合多环体系中,较大的环会失去芳香性,而较小的环则具有芳香性,因此我们通过控制特定环的芳香性实现了对电子结构的精确调节。在目标位置进行苯并氮化可对 HOMO-LUMO 间隙进行微调,从而使光电特性发生明显变化。我们开发了一种可扩展的合成方案,以生产各种 π 扩展衍生物。我们对这些化合物的结构、电子和光学特性进行了广泛表征。单晶 X 射线衍射证实了它们的分子结构,而理论计算则为观察到的实验趋势提供了见解。这些吲哚吲哚嗪类化合物在可见光谱范围内表现出鲜艳的色彩和荧光,而且与烯类化合物相比,它们的光氧化稳定性更强,因此有望在光电设备中得到实际应用。反应研究表明,亲电取代具有很高的区域选择性,突出了这些化合物的类吲哚行为,并为进一步官能化开辟了途径。总之,我们的工作为开发稳定、可调的光电应用有机材料提供了一个前景广阔的平台。通过利用以 Glidewell-Lloyd 规则为指导的合理分子设计,我们为有机电子学的分子设计提供了一条新的途径,从而有可能提高器件的性能和寿命。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Design, Synthesis, and Optoelectronic Properties of π-Expanded Indoloindolizines.
The development of stable and tunable polycyclic aromatic compounds (PACs) is crucial for advancing organic optoelectronics. Conventional polycyclic aromatic hydrocarbons (PAHs), such as acenes, often suffer from poor stability due to photooxidation and oligomerization, which are linked to their frontier molecular orbital energy levels. To address these limitations, we have designed and synthesized a new class of π-expanded indoloindolizines by merging indole and indolizine moieties into a single polycyclic framework. Guided by the Glidewell-Lloyd rule—which predicts that in fused polycyclic systems, larger rings lose aromaticity in favor of smaller ones—we achieved precise modulation of the electronic structure by controlling the aromaticity of specific rings. Benzannulation at targeted positions allowed fine-tuning of the HOMO-LUMO gap, leading to distinct shifts in optoelectronic properties. We developed a scalable synthetic protocol to produce a wide range of π-expanded derivatives. The structural, electronic, and optical properties of these compounds were extensively characterized. Single-crystal X-ray diffraction confirmed their molecular structure, while theoretical calculations provided insights into the observed experimental trends. These indoloindolizines exhibit vivid colors and fluorescence across the visible spectrum, and their enhanced stability against photooxidation compared to acenes makes them promising candidates for practical applications in optoelectronic devices. Reactivity studies demonstrated high regioselectivity in electrophilic substitutions, highlighting the indole-like behavior of these compounds and opening avenues for further functionalization. Overall, our work establishes indoloindolizines as a promising platform for the development of stable, tunable organic materials for optoelectronic applications. By leveraging rational molecular design guided by the Glidewell-Lloyd rule, we offer a new pathway for molecular design in organic electronics, potentially enhancing device performance and longevity.
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