新型推挽式联苯桥式发色团的分子工程，以实现卓越的非线性光学性质和芳香性调谐

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-07-14 DOI:10.1016/j.comptc.2025.115372

Hejing Sun

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引用次数: 0

摘要

本文首次设计并系统地研究了一系列具有强大推挽效应、独特芳香性和激发态特征的新型联苯（BPE）桥式发色团。利用多种先进的方法，本研究成功地揭示了新型BPE发色团的（反）芳香性、推挽效应、激发态特性和非线性光学（NLO）性质之间的关系。与目前流行的NLO共轭桥相比，独特的bpe桥接发色团具有双链共轭框架、更多π电子和更宽的共轭途径。值得注意的是，通过调节BPE共轭桥内融合（反）芳环的数量和排列，BPE发色团的电子结构、芳香性、激发态性质、电荷转移过程和NLO活性得到有效调节。令人兴奋的是，与代表性的发色团相比，DN-BPE5-AS和DN-BPE3-AS在CHCl3中分别具有显著的βprj值2229.7✕10−30和2184.5✕10−30 esu。值得注意的是，研究发现，在新型BPE发色团中，决定NLO活性的关键状态可能因其不同的（抗）芳香性和电子结构而变化。所有BPE发色团均表现出优异的光电微袋效应和光学整流效应。新型BPE发色团出色的NLO性能和独特的结构使其在芯片级光电集成电路中的应用前景广阔，推动了逻辑和数字技术的进步

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Molecular engineering of novel push-pull biphenylene bridge chromophores for achieving remarkable nonlinear optical properties and tuning aromaticity

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Molecular engineering of novel push-pull biphenylene bridge chromophores for achieving remarkable nonlinear optical properties and tuning aromaticity

A series of novel biphenylene (BPE) bridge chromophores possessing powerful push-pull effect, unique aromaticity and excited-state features has been designed and systematically investigated for the first time. Utilizing the multiple advanced methods, this study has successfully revealed the relationship between (anti)aromaticity, push-pull effects, excited-state characteristics, and nonlinear optical (NLO) properties of new BPE chromophores. The unique BPE-bridged chromophores have double-stranded conjugated framework, more π-electrons and broader conjugation pathways compared to the currently popular NLO conjugated bridges. Notably, by modulating the number and arrangement of fused (anti)aromatic rings within the BPE-conjugated bridge, the electronic structure, aromaticity, excited-state properties, charge transfer processes, and NLO activities of BPE chromophores are effectively tuned. Excitingly, compared to the representative chromophores, the DN-BPE5-AS and DN-BPE3-AS both have the remarkable β_prj values of 2229.7 ✕10⁻³⁰ and 2184.5✕10⁻³⁰ esu in CHCl₃, respectively. Significantly, it was found that the crucial state determining NLO activities in the novel BPE chromophore can vary due to the its diverse (anti)aromaticity and electronic structure. All BPE chromophores displayed excellent electro-optical Pockels and optical rectification effects. The outstanding NLO performance and unique structure of new BPE chromophores make them promising for applications in chip-scale optoelectronic integrated circuits, driving advancements in logic and digital technologies

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.