

FOLLOWUS
a.Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b.Handan Key Laboratory of Novel Nanobiomaterials, College of materials science and engineering, Hebei University of Engineering, Handan 056000, China
hanshuai@hebeu.edu.cn (S.H.)
xsz@mail.ipc.ac.cn (S.Z.X.)
sunjibin@mail.ipc.ac.cn (J.B.S.)
Received:11 November 2025,
Accepted:03 January 2026,
Online First:10 March 2026,
Published:05 April 2026
Scan QR Code
Wang, J.; Wang, P. R.; Cheng, X. W.; Zhou, S. Y.; Han, S.; Xiao, S. Z.; Sun, J. B.; Sun, C. H. Thiadiazoloquinoxaline-based donor-acceptor type copolymers towards ultrabroadband optical limiting. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3560-6
Jiang Wang, Pei-Ran Wang, Xiao-Wei Cheng, et al. Thiadiazoloquinoxaline-based Donor-Acceptor Type Copolymers towards Ultrabroadband Optical Limiting[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10.
Wang, J.; Wang, P. R.; Cheng, X. W.; Zhou, S. Y.; Han, S.; Xiao, S. Z.; Sun, J. B.; Sun, C. H. Thiadiazoloquinoxaline-based donor-acceptor type copolymers towards ultrabroadband optical limiting. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3560-6 DOI:
Jiang Wang, Pei-Ran Wang, Xiao-Wei Cheng, et al. Thiadiazoloquinoxaline-based Donor-Acceptor Type Copolymers towards Ultrabroadband Optical Limiting[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10. DOI: 10.1007/s10118-026-3560-6.
Construction of electron donor-acceptor (D-A) conjugated system is an established strategy for achieving reverse saturable absorption (RSA) and broadband optical limiting (OL). Nevertheless
organic materials exhibit OL ability across the visible to near-infrared-II spectra range remain scarce. Herein
a series of D-A type
π
-conjugated copolymers with ultra-narrow bandgaps (0.62–0.76 eV) and strong ICT absorption were synthesized by coupling electron-withdrawing block [1
2
5
]
thiadiazolo[3
4-
g
]
quinoxaline (TQ) with various electron-donating groups (thiophene
selenophene
bithiophene
di(thiophen-2-yl)ethene
and thienothiophene for
P1
–
P5
respectively).
Z
-scan experiments reveal that all copolymers exhibit RSA behaviours at both 532 and 1064 nm
while
P1
P3
and
P4
maintain RSA performance extending to 1600 nm. Among all copolymers
P5
exhibits the strongest RSA performance upon both 532 and 1064 nm laser pulses
with the highest nonlinear absorption coefficient (
β
eff
) of 51.5 and 49.4 cm·GW
−1
respectively
and the lowest OL onset fluence (
F
on
) of 0.31 and 0.38 J·cm
−2
respectively. In contrast
P4
shows optimal RSA property at 1600 nm laser pulse
with
β
eff
of 13.1 cm·GW
−1
and
F
on
of 1.43 J·cm
−2
respectively. Combining the results of
Z
-scan and UV-Vis-NIR experiments
it can be speculated that moderate ground-state absorption
rather than excessively strong absorption
favors superior RSA properties. This work offers valuable insights for designing copolymers with excellent RSA behavior
as well as presents a class of candidate material systems for ultrabroadband optical limiting.
Gadhwal, R.; Devi, A. A review on the development of optical limiters from homogeneous to reflective 1-D photonic crystal structures. Opt. Laser Technol. 2021 , 141 , 107144..
Li, P. L.; Wang, Y. H.; Shang, M.; Wu, L. F.; Yu, X. X. Enhanced optical limiting properties of graphene oxide-ZnS nanoparticles composites. Carbon 2020 , 159 , 1−8..
Dini, D.; Calvete, M. J. F.; Hanack, M. Nonlinear optical materials for the smart filtering of optical radiation. Chem. Rev. 2016 , 116 , 13043 − 13233..
Hirata, S.; Totani, K.; Yamashita, T.; Adachi, C.; Vacha, M. Large reverse saturable absorption under weak continuous incoherent light. Nat. Mater. 2014 , 13 , 938−946..
Li, Y.; Zheng, C.; Wang, S. T.; Liu, Y. J.; Fang, W. H.; Zhang, J. Record aluminum molecular rings for optical limiting and nonlinear optics. Angew. Chem. Int. Ed. 2022 , 61 , e202116563..
Zhao, W.; Zhang, H.; Wang, S.; Feng, L.; Wang, R.; Yuan, C. S.; Sun, J.; Liu Z.; Zhang H. L.; Sun C.; Shao, X. Chiral BN-heteroacenes embedded with B←N coordination: acid triggered reversible bond switching and optical limiting behavior. ACS Appl. Mater. Inter. 2025 , 17 , 47323−47336..
Qin, H.; Zhao, L.; Zheng, L.; Ma, Z.; Liao, M.; Sun, J.; Sun, C.; Chen, H. Non-alternant benzodifluoranthene tetraimides from 7,8,9,10-fluoranthene diimides: synthesis, structure, and optical-limiting properties. Chem. Eur. J. 2025 , 31 , e202403332..
Papadakis, I.; Bakandritsos, A .; Swain, A. K.; Szabo, T.; Couris, S. Effects of size and oxidation on the nonlinear optical response and optical limiting of graphene oxide Sheets. J. Phys. Chem. C 2020 , 124 , 11265−11273..
Ma, Z. Z.; Li, Q. H.; Wang, Z.; Gu, Z. G.; Zhang, J. Electrically regulating nonlinear optical limiting of metal-organic framework film. Nat. Commun. 2022 , 13 , 6347..
Wang, A.; Shen, X.; Wang, Q.; Cheng, L.; Zhu, W.; Shang, D.; Song, Y. Enhanced optical limiting and hydrogen evolution of graphene oxide nanohybrids covalently functionalized by covalent organic polymer based on porphyrin. Dalton Trans. 2021 , 50 , 7007−7016..
Wang, B.; Ma, B.; Wang, K.; Zhang, H.; Zhang, Z.; Song, T.; Wang, S.; Chen, M.; Li, S.; Wang, Q.; Zhang, H. L. Fractal Growth of 2D NbSe 2 for broadband nonlinear optical limiting. Adv. Funct. Mater. 2024 , 34 , 2401490..
Zheng, X.; Feng, M.; Zhan, H. Giant optical limiting effect in Ormosil gel glasses doped with graphene oxide materials. J. Mater. Chem. C 2013 , 1 , 6759−6766..
Liaros, N.; Aloukos, P.; Kolokithas-Ntoukas, A.; Bakandritsos, A.; Szabo, T.; Zboril, R.; Couris, S. Nonlinear optical properties and broadband optical power limiting action of graphene oxide colloids. J. Phys. Chem. C 2013 , 117 , 6842−6850..
Perry, J.; Mansour, K.; Lee, I. Y.; Wu, X. L.; Bedworth, P.; Chen, C. T.; Ng, D.; Marder, S.; Miles, P.; Wada, T. Organic optical limiter with a strongnonlinear absorptive response. Science 1996 , 273 , 1533−1536..
Zhang, K.; Wang, X.; Zhou, Z.; Guo J.; Liu, H.; Zhai,Y.; Yao, Y.; Yang, K.; Zeng, Z. Facile access to phosphorus ylide-fused heteroarenes possessing tunable optoelectronic properties and high nonlinear optical performances. Angew. Chem. Int. Ed. 2025 , 64 , e202418520..
Shang, H.; Song, G.; Wu, X.; Zhou, W.; Zhang, X.; Wang, Y.; Xiao, J.; Song, Y. Realizing excellent nonlinear optical performance in near-infrared region of helicene-functionalized arenes. Adv. Opt. Mater. 2025 , 13 , 2500047..
Lu, X.; Huo, Q.; Li, J.; Li, B.; Yu, X.; Sun, X.; Cheng, L.; Zhou, H.; Tian, Y.; Li, D. Elevating nonlinear optical response through D-electron modulation in metal-organic frameworks. Chem. Eur. J. 2025 , 31 , e202403564..
Hu, L.; Chen, Z.; Zhao, Z.; Chen, R.; Zhu, S.; Liu, R.; Zhu, H. Star-shaped Pt(II) complexes with excellent optical power limiting performance and their flexible optical limiters. Inorg. Chem. Front. 2025 , 12 , 6972−6984..
Dong, T.; Wen, X.; Li, J.; Wu, X.; Wang, C.; Zhou, W.; Yu, L.; Song, Y.; Wang, C.; Li J.; Bai, C. Simultaneous achievement of enhanced nonlinear optical absorption and nonlinear refraction in highly crystalline 2D covalent organic frameworks ultrathin films. Adv. Sci. 2025 , 12 , e2416170..
Luo, M. B.; Lai, H. D.; Huang, S. L.; Zhang, J.; Lin, Q. Pseudotetrahedral organotin-capped chalcogenidometalate supermolecules with optical limiting performance. J. Am. Chem. Soc. 2024 , 146 , 7690−7697..
Rose, A.; Lugmair, C. G.; Swager, T. M. Excited-state lifetime modulation in triphenylene-based conjugated polymers. J. Am. Chem. Soc. 2001 , 123 , 11298−11299..
Oleszak, C.; Schol, P. R.; Ritterhoff, C. L.; Krug, M.; Martin, M. M.; Bo, Y.; Meyer, B.; Clark, T.; Guld i, D. M.; Jux, N. Fused hexabenzocoronene-porphyrin conjugates with tailorable excited-state lifetimes. Angew. Chem. Int. Ed. 2024 , 63 , e202409363..
Wang, K.; Liang, J.; Li, Z.; Zhou, H.; Nie, C.; Deng, J.; Zhao, X.; Peng, X.; Chen, Z.; Peng, Z.; Huang, D.; Jang, H. S.; Kong, J.; Zou, Y. Design of experiments with the support of machine learning for process parameter optimization of all-small-molecule organic solar cells. FlexMat 2024 , 1 , 234−247..
Du, M.; Chen, Y.; Mai, M.; Fan, T.; Jin, Q.; Zhang, Y.; Duan, L. Understanding and modulating the horizontal orientations and short-range charge transfer excited states for high-performance narrowband emitters. FlexMat 2024 , 1 , 46−53..
Seo, S.; Park, J. Y.; Park, J. S.; Lee, S.; Choi, D. Y.; Kim, Y. H.; Kim, B. J. Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing. Nano Res. Energy 2024 , 3 , e9120088..
Luo, H.; Xiong, F.; Bai, H.; Wang, C.; Wang, Y.; Zhao, K.; Yan, J.; Zhang, Y.; Ding, J.; Wang, S.; Zhang, L.; Guo J.; Liu, Z. Multi-carbonyl naphthalene diimide polymer as a high-performance cathode for stable lithium-ion storage. Nano Res. Energy 2025 , 4 , e9120159.
[Xia, K.; Yao, Z.; Liu, Z.; Luo, S.; Xie, H.; Li, X.; Yao, X.; Liang, G.; Zhang, P. Hierarchical ionic networks in polymer electrolyte boost high-voltage solid-state Li batteries with stable interfaces and long cycling. Nano Res. Energy 2025 , 5 , e9120181.
Liu, Z.; Sun, J.; Yan, C.; Xie, Z.; Zhang, G.; Shao, X.; Zhang, D.; Zhou, S. Diketopyrrolopyrrole based donor–acceptor π-conjugated copolymers with near-infrared absorption for 532 and 1064 nm nonlinear optical materials. J. Mater. Chem. C 2020 , 8 , 12993−13000..
Sun, J.; Liu, Z.; Yan, C.; Sun, X.; Xie, Z.; Zhang, G.; Shao, X.; Zhang, D.; Zhou, S. Efficient Construction of Near-infrared absorption donor–acceptor copolymers with and without Pt(II)-incorporation toward broadband nonlinearoptical materials. ACS Appl. Mater. Interfaces 2019 , 12 , 2944−2951..
Wang, J.; Zhao, J.; Han, S.; Li, Y.; Zeng, W.; Sun, J.; Zhou, S. Significant enhancement of reverse saturable absorption ability via Pt(II) incorporation into the conjugated backbone of benzo[1,2-b:4,5-b′ ] dithiophene-based donor-Acceptor copolymers. Macromolecules 2024 , 57 , 1030−1037..
Nath, S.; Puthukkudi, A.; Mohapatra, J.; Biswal, B. P. Covalent organic frameworks as emerging nonlinear optical materials. Angew. Chem. Int. Ed. 2023 , 62 , e202218974..
Song, Y.; Sun, J.; He, X.; Liao, M.; Zhao, J.; Zeng, W.; Zhou S.; Chen, H. N-Doped nonalternant nanoribbons with excellent nonlinear optical performance. Angew. Chem. Int. Ed. 2023 , 62 , e202306418..
Ye, C.; Zhou, L.; Wang, X.; Liang, Z. Correction: Photon upconversion: from two-photon absorption (TPA) to triplet–triplet annihilation (TTA). Phys. Chem. Chem. Phys. 2016 , 18 , 7537−7537..
Zhang, M.; Xu, X.; Liu, J.; Jiang, Y.; Wang, J.; Dong, N.; Chen, C.; Zhu, B.; Liang, Y.; Fan, T.; Xu, J. All-organic composite films for high flexibility and giant nonlinear optical limiting responses. ACS Appl. Mater. Interfaces 2022 , 14 , 33787−33796..
Ahmed, S.; Xu, L.; Al Subri Ivan, M. N.; Zhu, M.; Qin, Y.; Sun, M.; Saha, S.; Shafayet, Y.; Huang, B.; Wong, W.-Y.; Tsang, Y. H. D-π-A-structured two-dimensional mercury(II)-acetylide frameworks for near-infrared switchable nonlinear optics and ultrafast photonics. Carbon 2025 , 238 , 120234..
Li, M.; Gong, C.; Du, J.; Ding, D.; Du, D.; Wang, D.; Jiang, J.; Li, T.; Zheng, C.; Yang, Y. F.; She, Y.; Jia, J. Donor–acceptor covalent organic frameworks films with ultralow band gaps to enhanced third-order nonlinear optical properties. ACS Mater. Lett. 2023 , 5 , 694−703..
Shi, M.; Huang, S.; Dong, N.; Liu, Z.; Gan, F.; Wang, J.; Chen, Y. Donor–acceptor type blends composed of black phosphorus and C 60 for solid-state optical limiters. Chem. Commun. 2018 , 54 , 366−369..
Dubuis, S.; Dellai, A.; Courdurié, C.; Owona, J.; Kalafatis, A.; Vellutini, L.; Genin, E.; Rodriguez, V.; Castet, F. Nonlinear optical responses of photoswitchable donor–acceptor stenhouse adducts. J. Am. Chem. Soc. 2023 , 145 , 10861−10871..
Hasegawa, T.; Ashizawa, M.; Aoyagi, K.; Masunaga, H.; Hikima, T.; Matsumoto, H. Thiadiazole-fused quinoxalineimide as an electron-deficient building block for N-type organic semiconductors. Org. Lett. 2017 , 19 , 3275−3278..
Yang, J.; Zhao, L.; Yin, Z.; Wang, J.; Zhao, Y.; Chen, H.; Liu, Y. Thiadiazoloquinoxaline-fused acenaphthenequinone imide: A highly electron-withdrawing acceptor for ambipolar semiconducting polymers with strong near-infrared absorption. Macromolecules 2021 , 54 , 3120−3129..
Steckler, T. T.; Henriksson, P.; Mollinger, S.; Lundin, A.; Salleo, A.; Andersson, M. R. Very low band gap thiadiazoloquinoxaline donor-acceptor polymers as multi-tool conjugated polymers. J. Am. Chem. Soc. 2014 , 136 , 1190−1193..
Wang, T.; Sun, R.; Yang, X. R.; Wu, Y.; Wang, W.; Li, Q.; Zhang, C. F.; Min, J. A Near-infrared polymer acceptor enables over 15% efficiency for all-polymer solar cells. Chinese J. Polym. Sci. 2022 , 40 , 877−888..
Wang, J.; Wang, P.; Li, Y.; Cheng, X.; Zhou, S.; Han, S.; Sun, J.; Sun, C. Low-bandgap organic conjugated copolymers with ultraBroadband optical limiting properties extending to near-infrared-II. ACS Macro Lett. 2025 , 14 , 1081−1087..
Sheik-Bahae, M.; Said, A. A.; van Stryland, E. W. High-sensitivity, single-beam n 2 measurements. Opt. Lett. 1989 , 14 , 955−957..
Sheik-Bahae, M.; Said, A. A.; Wei, T. H.; Hagan, D. J.; Van Stryland, E. W. Sensitive measurement of optical nonlinearities using a single beam. IEEE J. Quantum Electron 2002 , 26 , 760−769..
Li, D. J.; Li, Q. H.; Wang, Z. R.; Ma, Z. Z.; Gu, Z. G.; Zhang, J. Interpenetrated metal-porphyrinic framework for enhanced nonlinear optical limiting. J. Am. Chem. Soc. 2021 , 143 , 17162−17169..
0
Views
0
Downloads
0
CSCD
Publicity Resources
Related Articles
Related Author
Related Institution
京公网安备11010802046900号