应用化学 ›› 2025, Vol. 42 ›› Issue (6): 785-792.DOI: 10.19894/j.issn.1000-0518.250136

• 研究论文 • 上一篇    下一篇

具有扭曲结构的基于苯并噻二唑单元的D-A-D型有机荧光防伪材料

焦海龙1,2, 苗俊辉1(), 刘俊1,2()   

  1. 1.中国科学院长春应用化学研究所,高分子科学与技术全国重点实验室,长春 130022
    2.中国科学技术大学应用化学与工程学院,合肥 230026
  • 收稿日期:2025-04-01 接受日期:2025-05-07 出版日期:2025-06-01 发布日期:2025-07-01
  • 通讯作者: 苗俊辉,刘俊
  • 基金资助:
    国家自然科学基金(U24A2080)

D-A-D Type Organic Fluorescent Anti-Counterfeiting Materials Based on Benzothiadiazole Unit with Twisted Structure

Hai-Long JIAO1,2, Jun-Hui MIAO1(), Jun LIU1,2()   

  1. 1.State Key Laboratory of Polymer Science and Technology,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China
    2.School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026,China
  • Received:2025-04-01 Accepted:2025-05-07 Published:2025-06-01 Online:2025-07-01
  • Contact: Jun-Hui MIAO,Jun LIU
  • About author:liujun@ciac.ac.cn
    jhmiao@ciac.ac.cn
  • Supported by:
    the National Natural Science Foundation of China(U24A2080)

摘要:

防伪和信息加密技术是保障社会经济安全的重要支撑。 有机光致荧光材料因其可调的光物理性质、良好的加工性以及易于操作和识别等特点,在防伪领域展示出巨大潜力。 然而,目前国内大多数有机荧光材料仍局限于低端商品防伪,在高安全性防伪(如货币、证件等)应用中存在明显不足。 其中,高性能绿光材料的开发尤为关键,但面临“显色深度-发光性能”难以协同优化的挑战: 强绿光发射通常需要平面共轭分子骨架以增强发光效率,而浅色外观则要求扭曲分子结构以增大斯托克斯位移并减少可见光区吸收。 针对这一矛盾,本工作设计并合成了一系列以双甲基苯并噻二唑(BTD)为受体中心核,以咔唑、联萘、螺芴和苯基芴为给体端基的D-A-D型分子,通过甲基引入产生的空间位阻效应,构建扭曲分子构型,实现大的斯托克斯位移。 其中,基于咔唑端基的分子BT-Cz具有可见光弱吸收、发射波长在绿光区(503 nm)、斯托克斯位移超过100 nm,展现出优异的浅色防伪性能。 此外,百克级放大合成和良好的抗光漂白性能够满足浅色绿光防伪材料的实际应用,证明了该材料的产业化潜力。

关键词: 荧光防伪, 光致发光, 有机荧光材料, 斯托克斯位移

Abstract:

Anti-counterfeiting and information encryption technologies serve as crucial safeguards for socio-economic security. Organic photoluminescent (PL) materials have demonstrated significant potential in anti-counterfeiting applications due to their tunable photophysical properties, excellent processability, and ease of operation and identification. However, most current domestic organic fluorescent materials remain confined to low-end commodity anti-counterfeiting, exhibiting notable deficiencies in high-security applications such as currency and official documents. The development of high-performance green-emitting materials is particularly critical yet faces the challenge of balancing “color depth-luminescence performance”: strong green emission typically requires planar conjugated molecular frameworks to enhance luminescence efficiency, while light-colored appearance demands twisted molecular structures to increase Stokes shift and reduce visible light absorption. To address this dilemma, this paper designed and synthesized a series of D-A-D type molecules featuring dimethylbenzothiadiazole (BTD) as the central acceptor core and carbazole, binaphthyl, spirofluorene, or phenylfluorene as donor end-groups. By introducing methyl groups to create steric hindrance effects, twisted molecular configurations were constructed to achieve large Stokes shifts. Notably, the carbazole-end-capped molecule BT-Cz exhibits weak visible light absorption, green emission at 503 nm, and a Stokes shift exceeding 100 nm, demonstrating outstanding light-colored anti-counterfeiting performance. Furthermore, its scalability to hundred-gram synthesis and excellent photobleaching resistance meet the practical requirements for light-colored green-emitting anti-counterfeiting materials, highlighting its industrial potential.

Key words: Fluorescent anti-counterfeiting, Photoluminescence, Organic fluorescent materials, Stokes shift

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