Tuning charge transfer pathways through chiral binaphthyl structural engineering: Molecular design and versatile applications

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2026-06-01 Epub Date: 2026-01-14 DOI:10.1016/j.dyepig.2026.113574

Xuteng Lang , Xin Meng , Xiaohan Zheng , Jian Tang , Ensheng Zhang , Yuanchun He , Xiaoxiang Zhang , Ziping Cao , X. Lang , X. Meng , X. Zheng , J. Tang , E. Zhang , Y. He , Z. Cao , Z. Zhang

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引用次数: 0

Abstract

Structural engineering is pivotal for modulating emission mechanisms in organic luminescent materials. By introducing twisted electron-donating groups and varying the modes of chiral scaffold incorporation, we present the synthesis and analysis of two novel luminophores, (S)-BiNpIm and (S,S)-EtBiNpIm. Photophysical studies reveal marked differences in emission wavelengths, a distinction attributable to fundamental variations in their emission pathways. Single-crystal X-ray diffraction and theoretical calculations provide compelling evidence for both through-bond charge transfer (TBCT) and through-space charge transfer (TSCT) processes. Notably, the spatially parallel arrangement of electron donors in (S,S)-EtBiNpIm interrupts conventional TBCT pathways, resulting in distinctive TSCT behavior. Both compounds display pronounced chiroptical activity in the excited state, as evidenced by circularly polarized luminescence measurements. Furthermore, these materials exhibit reversible, stimuli-responsive luminescence modulation upon acid-base treatment, highly sensitive acid detection in organic phases, and the capacity to serve as efficient emitters in LED devices. Collectively, these findings offer valuable insight into the fine-tuning of chiral luminescence via strategic molecular engineering of charge transfer processes, thereby advancing the development of responsive chiral materials for optoelectronic and sensing applications.

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通过手性二萘基结构工程调整电荷转移途径：分子设计和多功能应用

结构工程是调节有机发光材料发射机制的关键。通过引入扭曲给电子基团和改变手性支架结合模式，我们合成并分析了两种新型发光基团(S)-BiNpIm和（S，S）-EtBiNpIm。光物理研究揭示了发射波长的显著差异，这种差异可归因于它们发射路径的基本变化。单晶x射线衍射和理论计算为通过键电荷转移（TBCT）和通过空间电荷转移（TSCT）过程提供了令人信服的证据。值得注意的是，（S，S）-EtBiNpIm中电子给体的空间平行排列中断了传统的TBCT途径，导致了独特的TSCT行为。这两种化合物在激发态下都显示出明显的旋光活性，圆偏振发光测量证明了这一点。此外，这些材料在酸碱处理下表现出可逆的，刺激响应的发光调制，在有机相中高度敏感的酸检测，以及在LED器件中作为高效发射器的能力。总的来说，这些发现为通过电荷转移过程的战略性分子工程对手性发光进行微调提供了有价值的见解，从而推进了用于光电和传感应用的响应性手性材料的开发。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.