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

doi:10.19894/j.issn.1000-0518.250136

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (6): 785-792.DOI: 10.19894/j.issn.1000-0518.250136

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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.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)

1. .pdf(1149KB)

Abstract

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

CLC Number:

O649

Hai-Long JIAO, Jun-Hui MIAO, Jun LIU. D-A-D Type Organic Fluorescent Anti-Counterfeiting Materials Based on Benzothiadiazole Unit with Twisted Structure[J]. Chinese Journal of Applied Chemistry, 2025, 42(6): 785-792.

Figures/Tables 5

Fig.1 Synthetic route of fluorescent molecules

Fig.2 The optimized geometries and the Kohn-Sham LUMO/HOMOs of BT-Cz， BT-Ni， BT-SF and BT-PhF

Fig.3 UV-Vis absorption spectra in solutions （A）， UV-Vis absorption spectra in films （B）， PL spectra in solutions （C）， PL spectra in films （D） and transient photoluminescence decay curves （E） of the fluorescent molecules

Table 1 Photophysical characteristics of BT-Cz， BT-Ni， BT-SF and BT-PhF

	$λ a b s, s o l a$ /nm	$λ a b s, f i l m b$ /nm	$λ f l u o, s o l a$ /nm	$λ f l u o, f i l m b$ /nm
BT-Cz	348	352	503	504
BT-Ni	349	360	465	461
BT-PhF	369	372	483	475
BT-SF ^c	373	375	478	477

Table 1 Photophysical characteristics of BT-Cz， BT-Ni， BT-SF and BT-PhF

	$λ a b s, s o l a$ /nm	$λ a b s, f i l m b$ /nm	$λ f l u o, s o l a$ /nm	$λ f l u o, f i l m b$ /nm
BT-Cz	348	352	503	504
BT-Ni	349	360	465	461
BT-PhF	369	372	483	475
BT-SF ^c	373	375	478	477

Fig.4 UV-Vis （A） and PL （B） spectra of BT-Cz before and after irradiation in films

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

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