Role of exciton delocalization in chiroptical properties of benzothiadiazole carbon nanohoops†

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Kovida Kovida, Juraj Malinčík, Carlos M. Cruz, Araceli G. Campaña and Tomáš Šolomek
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Abstract

Development of chiral organic materials with a strong chiroptical response is crucial to advance technologies based on circularly polarized luminescence, enantioselective sensing, or unique optical signatures in anti-counterfeiting. The progress in the field is hampered by the lack of structure–property relationships that would help designing new chiral molecules. Here, we address this challenge by synthesis and investigation of two chiral macrocycles that integrate in their structure a pseudo-meta [2.2]paracyclophane with planar chirality and a highly fluorescent benzothiadiazole. Both compounds display remarkably red-shifted fluorescence with high quantum yields and large Stokes shifts. They differ in the extent of π-electron conjugation that allowed, for the first time, systematic examination of the effect of exciton delocalization on the absorption and luminescence of circularly polarized light. By a combination of steady-state spectroscopy and quantum chemical calculations, we constructed a unique structure–property relationship offering critical insights that will aid and abet the development of robust design guidelines for materials with strong electronic circular dichroism or circularly polarized luminescence of exceptional brightness.

Abstract Image

Abstract Image

激子离域在苯并噻唑碳纳米环热学性质中的作用
具有强手性响应的手性有机材料的开发对于基于圆偏振发光、对映选择性传感或独特光学特征的防伪技术的发展至关重要。由于缺乏有助于设计新的手性分子的结构-性质关系,这一领域的进展受到阻碍。在这里,我们通过合成和研究两个手性大环来解决这一挑战,这两个手性大环在其结构中整合了具有平面手性的伪元[2.2]副环烷和高荧光苯并噻二唑。这两种化合物都显示出显著的红移荧光,具有高量子产率和大的斯托克斯位移。它们的π-电子共轭程度不同,首次系统地研究了激子离域对圆偏振光的吸收和发光的影响。通过结合稳态光谱学和量子化学计算,我们构建了一个独特的结构-性质关系,提供了关键的见解,这将有助于和教唆性地开发具有强电子圆二色性或圆偏振发光的材料的强大设计指南。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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