Molecular engineering of sterically-isolated spherical chromophores for high-performance second order nonlinear optical polymers

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-07-03 DOI:10.1016/j.dyepig.2025.112988

Zefan Duan , Fuyang Huo , Bujia Liu , Zuo Zhang , Abdul Rahman , Zhuo Chen , Xiaoping Yang , Cailin Fu , Shuhui Bo

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引用次数: 0

Abstract

Four novel chromophores have been designed and synthesized, consisting of julolidine electron donors, tricyanofuran (TCF) or trifluoromethyl-phenyl-tricyanofuran (CF₃-Ph-TCF) as electron acceptors, and modified diene π-bridges. Based on the chromophores BHD-1 and BHD-2, benzene derivatives containing three 3,5-bis(trifluoromethyl) substituents were incorporated into π-electron bridge to obtain BHD-3 and BHD-4. Thermal stability, optical properties and microscopic nonlinearity calculated by density functional theory (DFT) of chromophores were examined to explore structure-property relationships. Macroscopic electro-optic (EO) activity was also evaluated. As the concentration of doped chromophores increases, the EO coefficient of BHD-4/PMMA becomes higher, reaching a maximum of 78 p.m./V. Compared with the host-guest system, the EO activity of the neat BHD-4 film without and with a titanium dioxide (TiO₂) charge-blocking layer have been significantly improved, particularly the latter achieving a maximum EO coefficient of 112 p.m./V. The results demonstrate that the introduction of 3,5-bis(trifluoromethyl) benzene derivatives as auxiliary isolation groups can modify the chromophore into a more spherical configuration, thereby enhancing EO performance.

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高性能二阶非线性光学聚合物空间分离球形发色团的分子工程

设计并合成了四种新型发色团，由苯胺类电子给体、三氟甲基苯基三氰呋喃（TCF）或三氟甲基苯基三氰呋喃（CF3-Ph-TCF）为电子受体和修饰的二烯π桥组成。以BHD-1和BHD-2为发色团，将含有3个3,5-二（三氟甲基）取代基的苯衍生物纳入π电子桥，得到了BHD-3和BHD-4。利用密度泛函理论（DFT）计算了发色团的热稳定性、光学性质和微观非线性，探讨了结构-性能之间的关系。并对宏观电光（EO）活性进行了评价。随着掺杂发色团浓度的增加，BHD-4/PMMA的EO系数越来越高，最大值为78 pm /V。与主客体体系相比，无二氧化钛（TiO2）电荷阻挡层和有二氧化钛（TiO2）电荷阻挡层的整齐BHD-4膜的EO活性均有显著提高，其中二氧化钛（TiO2）电荷阻挡层的EO系数最高可达112 pm /V。结果表明，引入3,5-双（三氟甲基）苯衍生物作为辅助隔离基团，可以将发色团修饰成更球形的结构，从而提高EO性能。

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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.