A Terbium Coordination Cross-linked Tough Metallo-elastomer Showing Fluorochromism in Response to Multistimuli

Ming-Hui Wei; Ying-Ying Xu; Qiu-Li Tan; Bo Liu; Yi-Jing Nie; Geng-Sheng Weng

doi:10.1007/s10118-025-3458-8

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A Terbium Coordination Cross-linked Tough Metallo-elastomer Showing Fluorochromism in Response to Multistimuli

RESEARCH ARTICLE | Updated：2025-12-03

- A Terbium Coordination Cross-linked Tough Metallo-elastomer Showing Fluorochromism in Response to Multistimuli
- Chinese Journal of Polymer Science Vol. 43, Issue 12, Pages: 2349-2361(2025)
- Affiliations：
  
  a.School of Materials Science and Chemical Engineering, State Key Laboratory Base of Novel Functional Materials and Preparation Science, Ningbo University, Ningbo 315211, China
  b.Institute of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
- Author bio：
  
  nieyijing@ujs.edu.cn (Y.J.N.)
  wenggengsheng@nbu.edu.cn (G.S.W.)
- Funds：
- DOI：10.1007/s10118-025-3458-8
  CLC： [M
- Received：13 August 2025，
  
  Accepted：18 September 2025，
  
  Published Online：19 November 2025，
  
  Published：15 December 2025
- Accepted：
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Wei, M. H.; Xu, Y. Y.; Tan, Q. L.; Liu, B.; Nie, Y. J.; Weng, G. S. A Terbium coordination cross-linked tough metallo-elastomer showing fluorochromism in response to multistimuli. Chinese J. Polym. Sci. 2025, 43, 2349–2361

Ming-Hui Wei, Ying-Ying Xu, Qiu-Li Tan, et al. A Terbium Coordination Cross-linked Tough Metallo-elastomer Showing Fluorochromism in Response to Multistimuli[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2349-2361.
Wei, M. H.; Xu, Y. Y.; Tan, Q. L.; Liu, B.; Nie, Y. J.; Weng, G. S. A Terbium coordination cross-linked tough metallo-elastomer showing fluorochromism in response to multistimuli. Chinese J. Polym. Sci. 2025, 43, 2349–2361 DOI： 10.1007/s10118-025-3458-8.

Ming-Hui Wei, Ying-Ying Xu, Qiu-Li Tan, et al. A Terbium Coordination Cross-linked Tough Metallo-elastomer Showing Fluorochromism in Response to Multistimuli[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2349-2361. DOI： 10.1007/s10118-025-3458-8.

摘要

A Tb-carboxyl-imidazole coordination-crosslinked carboxylated nitrile butadiene rubber (XNBR) elastomer that exhibits high mechanical robustness

fluorochromism

and white-light emission is reported. This coordination cross-linked tough elastomer paves a new way for fabricating soft devices and sensors

where optical information displays and optical signal responses are required.

Abstract

Herein

we reported a Tb-carboxyl-imidazole coordination-crosslinked carboxylated nitrile butadiene rubber (XNBR) elastomer design that exhibits high mechanical robustness

fluorochromism

and white-light emission. Imidazole (Im)

a toughening

sensitizing

and self-emissive ligand

highly intensified the f

luorescence emission

remarkably toughened the elastomer

and imparted multistimuli responsiveness to the elastomer. The Tb

ions acted as cross-linking centers and provided high-temperature sensitivity of fluorescence emission (more sensitive than Eu

ions). The as-prepared XNBR/Tb/Im elastomer

with excellent puncture resistance

exhibited an ultimate extensibility of about 3100% and the highest tensile strength of 22 MPa. Experimental and theoretical investigations have demonstrated that Tb

ions are more likely to interact with Im ligands with increasing amounts of Im. The number of coordination cross-links with higher cross-linking functionalities showed an increasing trend during stretching. The elastomer exhibited an excitation wavelength and temperature-dependent green emission. By introducing red-emissive Eu

into the elastomer

a white-light-emitting XNBR/Tb/Eu/Im elastomer with chemo-fluorochromism was fabricated. The XNBR/Tb/Eu/Im elastomer exhibited stable white-light emission during both heating and stretching. Changing the temperature only resulted in a variation in the intensity of the white light. We demonstrated the potential applications of these elastomers in patterning and information anti-counterfeiting/encryption. This coordination crosslinked tough elastomer with fluorochromism and white-light emission paves a new way to fabricate soft devices and sensors

where optical information displays and optical signal responses are required.

关键词

Keywords

references

Mannsfeld, S. C.; Tee, B. C.; Stoltenberg, R. M.; Chen, C. V. H.; Barman, S.; Muir, B. V.; Sokolov, A. N.; Reese, C.; Bao, Z. Highly sensitive flexible pressure sensors with microstructured rubber dielectric layers. Nat. Mater. 2010 , 9 , 859−864..

Takei, K.; Takahashi, T.; Ho, J. C.; Ko, H.; Gillies, A. G.; Leu, P. W.; Fearing, R. S.; Javey, A. Nanowire active-matrix circuitry for low-voltage macroscale artificial skin. Nat. Mater. 2010 , 9 , 821−826..

Cao, Y.; Tan, Y. J.; Li, S.; Lee, W. W.; Guo, H.; Cai, Y.; Wang, C.; Tee, B. C. K. Self-healing electronic skins for aquatic environments. Nat. Electro. 2019 , 2 , 75−82..

Núñez, C. G.; Navaraj, W. T.; Polat, E. O.; Dahiya, R. Energy-autonomous, flexible, and transparent tactile skin. Adv. Funct. Mater. 2017 , 27 , 1606287..

Kim, J.; Campbell, A. S.; de Ávila, B. E. F.; Wang, J. Wearable biosensors for healthcare monitoring. Nat. Biotechnol. 2019 , 37 , 389−406..

Hua, Q.; Sun, J.; Liu, H.; Bao, R.; Yu, R.; Zhai, J.; Pan, C.; Wang, Z. L. Skin-inspired highly stretchable and conformable matrix networks for multifunctional sensing. Nat. Commun. 2018 , 9 , 244..

Zeng, S.; Zhang, D.; Huang, W.; Wang, Z.; Freire, S. G.; Yu, X.; Smith, A. T.; Huang, E. Y.; Nguon, H.; Sun, L. Bio-inspired sensitive and reversible mechanochromisms via strain-dependent cracks and folds. Nat. Commun. 2016 , 7 , 11802..

Nakajima, R.; Lajbner, Z.; Kuba, M. J.; Gutnick, T.; Iglesias, T. L.; Asada, K.; Nishibayashi, T.; Miller, J. Squid adjust their body color according to substrate. Sci. Rep. 2022 , 12 , 5227..

Teyssier, J.; Saenko, S. V.; van der Marel, D.; Milinkovitch, M. C. Photonic crystals cause active colour change in chameleons. Nat. Commun. 2015 , 6 , 6368..

Yang, W.; Sherman, V. R.; Gludovatz, B.; Schaible, E.; Stewart, P.; Ritchie, R. O.; Meyers, M. A. On the tear resistance of skin. Nat. Commun. 2015 , 6 , 6649..

[Sisanth, K. S.; Thomas, M. G.; Abraham, J.; Thomas, S., 1 - general introduction to rubber compounding. In Progress in rubber nanocomposites , Thomas, S.; Maria, H. J., Eds. Woodhead Publishing, 2017 , pp. 1-39..

Weng, G.; Huang, G.; Qu, L.; Nie, Y.; Wu, J. Large-scale orientation in a vulcanized stretched natural rubber network: proved by in situ synchrotron x -ray diffraction characterization. J. Phys. Chem. B 2010 , 114 , 7179−7188..

Li, H.; Yang, L.; Weng, G.; Xing, W.; Wu, J.; Huang, G. Toughening rubbers with a hybrid filler network of graphene and carbon nanotubes. J. Mater. Chem. A 2015 , 3 , 22385−22392..

Huang, X.; Zhang, A.; Tan, Q.; Gou, K.; Chen, Y.; Nie, Y.; Weng, G. Highly stretchable and self-healable tough polymer elastomer through Dy 3+ and Cu 2+ coordination cross-linking. Macromolecules 2024 , 57 , 963−975..

Zhou, X.; Wang, L.; Wei, Z.; Weng, G.; He, J. An adaptable tough elastomer with moisture-triggered switchable mechanical and fluorescent properties. Adv. Funct. Mater. 2019 , 29 , 1903543..

Wan, X.; Gou, K.; Liu, Y.; Tang, J.; Tan, Q.; Weng, G. One-pot and fast synthesis of hydrogels with photoswitchable dynamic coordination cross-linking for tunable healing, photopatterning, and light sensing. Macromolecules 2025 , 58 , 4375−4384..

Chen, Y.; Tang, Z.; Liu, Y.; Wu, S.; Guo, B. Mechanically robust, self-healable, and reprocessable elastomers enabled by dynamic dual cross-links. Macromolecules 2019 , 52 , 3805−3812..

Yang, L.; Wang, C.; Xu, Y.; Luo, X.; Chang, G. Facile synthesis of recyclable Zn(II)-metallosupramolecular polymers and the visual detection of tensile strength and glass transition temperature. Polym. Chem. 2018 , 9 , 2721−2726..

Lai, J. C.; Jia, X. Y.; Wang, D. P.; Deng, Y. B.; Zheng, P.; Li, C. H.; Zuo, J. L.; Bao, Z. Thermodynamically stable whilst kinetically labile coordination bonds lead to strong and tough self-healing polymers. Nat. Commun. 2019 , 10 , 1164..

Hong, G.; Zhang, H.; Lin, Y.; Chen, Y.; Xu, Y.; Weng, W.; Xia, H. Mechanoresponsive healable metallosupramolecular polymers. Macromolecules 2013 , 46 , 8649−8656..

Zhang, Q.; Niu, S.; Wang, L.; Lopez, J.; Chen, S.; Cai, Y.; Du, R.; Liu, Y.; Lai, J. C.; Liu, L.; Li, C. H.; Yan, X.; Liu, C.; Tok, J. B. H.; Jia, X.; Bao, Z. An elastic autonomous self-healing capacitive sensor based on a dynamic dual crosslinked chemical system. Adv. Mater. 2018 , 30 , 1801435..

Zhang, L.; Liu, Z.; Wu, X.; Guan, Q.; Chen, S.; Sun, L.; Guo, Y.; Wang, S.; Song, J.; Jeffries, E. M.; He, C.; Qing, F. L.; Bao, X.; You, Z. A highly efficient self-healing elastomer with unprecedented mechanical properties. Adv. Mater. 2019 , 31 , 1901402..

Chen, S. Y.; Zhao, Z. H.; Li, C. H.; Li, Q. Responsive materials based o n coordination bonds. Respons. Mater. 2023 , 1 , e20230011..

Kong, Q.; Tan, Y.; Zhang, H.; Zhu, T.; Wang, X. Coordination-enhanced ionic elastomers: Durable, self-healing, and multimodal sensors for wearable electronics and robotics. Chem. Eng. J. 2025 , 503 , 158415..

Khare, E.; Holten-Andersen, N.; Buehler, M. J. Transition-metal coordinate bonds for bioinspired macromolecules with tunable mechanical properties. Nat. Rev. Mater. 2021 , 6 , 421−436..

Grindy, S. C.; Learsch, R.; Mozhdehi, D.; Cheng, J.; Barrett, D. G.; Guan, Z.; Messersmith, P. B.; Holten-Andersen, N. Control of hierarchical polymer mechanics with bioinspired metal-coordination dynamics. Nat. Mater. 2015 , 14 , 1210−1216..

Park, H.; Kang, T.; Kim, H.; Kim, J. C.; Bao, Z.; Kang, J. Toughening self-healing elastomer crosslinked by metal–ligand coordination through mixed counter anion dynamics. Nat. Commun. 2023 , 14 , 5026..

Mozhdehi, D.; Neal, J. A.; Grindy, S. C.; Cordeau, Y.; Ayala, S.; Holten-Andersen, N.; Gua n, Z. Tuning dynamic mechanical response in metallopolymer networks through simultaneous control of structural and temporal properties of the networks. Macromolecules 2016 , 49 , 6310−6321..

Kawamoto, K.; Grindy, S. C.; Liu, J.; Holten-Andersen, N.; Johnson, J. A. Dual role for 1,2,4,5-tetrazines in polymer networks: Combining Diels–Alder reactions and metal coordination to generate functional supramolecular gels. ACS Macro Lett. 2015 , 4 , 458−461..

Ma, C.; Wang, Y.; Jiang, Z.; Cao, Z.; Yu, H.; Huang, G.; Wu, Q.; Ling, F.; Zhuang, Z.; Wang, H.; Zheng, J.; Wu, J. Wide-range linear viscoelastic hydrogels with high mechanical properties and their applications in quantifiable stress-strain sensors. Chem. Eng. J. 2020 , 399 , 125697..

Filippidi, E.; Cristiani, T. R.; Eisenbach, C. D.; Waite, J. H.; Israelachvili, J. N.; Ahn, B. K.; Valentine, M. T. Toughening elastomers using mussel-inspired iron-catechol complexes. Science 2017 , 358 , 502−505..

Wei, Z.; Duan, H.; Weng, G.; He, J. Metals in polymers: hybridization enables new functions. J. Mater. Chem. C 2020 , 8 , 15956−15980..

Liu, J.; Huang, Y. S.; Liu, Y.; Zhang, D.; Koynov, K.; Butt, H. J.; Wu, S. Reconfiguring hydrogel assemblies using a photocontrolled metallopolymer adhesive for multiple customized functions. Nat. Chem. 2024 , 16 , 1024−1033..

Zeng, X.; Zhang, Z.; Huang, Y. S.; Fan, J.; Peng, X.; Wu, S.; Sun, W. Photoresponsive Ru metalloprodrug assemblies: red-light-controlled self-delivery systems for enhanced anticancer phototherapy. Adv. Funct. Mater. 2024 , 34 , 2315885..

Lu, W.; Le, X.; Zhang, J.; Huang, Y.; Chen, T. Supramolecular shape memory hydrogels: a new bridge between stimuli-responsive polymers and supramolecular chemistry. Chem. Soc. Rev. 2017 , 46 , 1284−1294..

Wei, S.; Li, Z.; Lu, W.; Liu, H.; Zhang, J.; Chen, T.; Tang, B. Z. Multicolor fluorescent polymeric hydrogels. Angew. Chem. Int. Ed. 2021 , 60 , 8608−8624..

Li, Z.; Hou, Z.; Fan, H.; Li, H. Organic–inorganic hierarchical self-assembly into robust luminescent supramolecular hydrogel. Adv. Funct. Mater. 2017 , 27 , 1604379..

Surender, E. M.; Bradberry, S. J.; Bright, S. A.; McCoy, C. P.; Williams, D. C.; Gunnlaugsson, T. Luminescent lanthanide cyclen-based enzymatic assay capable of diagnosing the onset of catheter-associated urinary tract infections both in solution and within polymeric hydrogels. J. Am. Chem. Soc. 2017 , 139 , 381−388..

Xu, Z.; Fu, J. Programmable and reversible 3D-/4D-shape-morphing hydrogels with precisely defined ion coordination. ACS Appl. Mater. Interfaces 2020 , 12 , 26476−26484..

Yang, L.; Zhang, G.; Zheng, N.; Zhao, Q.; Xie, T. A metallosupramolecular shape-memory polymer with gradient thermal plasticity. Angew. Chem. Int. Ed. 2017 , 56 , 12599−12602..

Zhang, X.; Liu, J.; Zhang, Z.; Wu, S.; Tang, Z.; Guo, B.; Zhang, L. Toughening elastomers using a mussel-inspired multiphase design. ACS Appl. Mater. Interfaces 2018 , 10 , 23485−23489..

Jia, X. Y.; Mei, J. F.; Lai, J. C.; Li, C. H.; You, X. Z. A highly stretchable polymer that can be thermally healed at mild temperature. Macromol. Rapid Commun. 2016 , 37 , 952−956..

Wang, Z.; Xie, C.; Yu, C.; Fei, G.; Wang, Z.; Xia, H. A facile strategy for self-healing polyurethanes containing multiple metal–ligand bonds. Macromol. Rapid Commun. 2018 , 39 , 1700678..

Lai, J. C.; Li, L.; Wang, D. P.; Zhang, M. H.; Mo, S. R.; Wang, X.; Zeng, K. Y.; Li, C. H.; Jiang, Q.; You, X. Z.; Zuo, J. L. A rigid and healable polymer cross-linked by weak but abundant Zn(II)-carboxylate interactions. Nat. Commun. 2018 , 9 , 2725..

Beck, J. B.; Ineman, J. M.; Rowan, S. J. Metal/ligand-induced formation of metallo-supramolecular polymers. Macromolecules 2005 , 38 , 5060−5068..

Rao, Y. L.; Chortos, A.; Pfattner, R.; Lissel, F.; Chiu, Y. C.; Feig, V.; Xu, J.; Kurosawa, T.; Gu, X.; Wang, C.; He, M.; Chung, J. W.; Bao, Z. Stretchable self-healing polymeric dielectrics cross-linked through metal–ligand coordination. J. Am. Chem. Soc. 2016 , 138 , 6020−6027..

Yang, S. M.; Zhou, S.; Yuan, J. Y. Self-healing elastomers and coatings via metal coordination bonds. Chem. Eur. J. 2025 , 31 , e202404038..

Wei, Z.; Thanneeru, S.; Margaret Rodriguez, E.; Weng, G.; He, J. Adaptable Eu-containing polymeric films with dynamic control of mechanical properties in response to moisture. Soft Matter 2020 , 16 , 2276−2284..

Yin, Q. Y.; Dai, C. H.; Chen, H.; Gou, K.; Guan, H. Z.; Wang, P. H.; Jiang, J. T.; Weng, G. S. Tough double metal-ion cross-linked elastomers with temperature-adaptable self-healing and luminescence properties. Chinese J. Polym. Sci. 2021 , 39 , 554−565..

Tan, Q. L.; Gou, K.; Tang, J. Z.; Wei, M. H.; Wang, C.; Nie, Y. J.; Weng, G. S. Highly stretchable and tunable thermo-fluorochromic polymer elastomer through Eu 3+ dynamic coordination cross-linking. Chinese J. Polym. Sci. 2024 , 42 , 1449−1458..

Kumpfer, J. R.; Rowan, S. J. Thermo-, photo-, and chemo-responsive shape-memory properties from photo-cross-linked metallo-supramolecular polymers. J. Am. Chem. Soc. 2011 , 133 , 12866−12874..

Li, C.; Su, X.; Cao, C.; Li, X.; Zou, M. A dynamic supramolecular elastomer with high mechanical stability guided by intra-ring coordination stabilization structures and interchain coordination competition sacrifice strategies. Macromolecules 2025 , 58 , 6111−6123..

Zhao, D.; Yue, C.; Li, Q.; Guo, L.; Yang, J.; Li, H. Self-healing luminescent elastomers with ultrahigh mechanical strength, superior toughness, and stimuli-responsive luminescence. ACS Appl. Polym. Mater. 2023 , 5 , 9375−9384..

Zhao, D.; Guo, L.; Li, Q.; Yue, C.; Han, B.; Liu, K.; Li, H. Multi-functional lanthanide metallopolymer: self-healing and photo-stimuli-responsive dual-emitting luminescence for diverse applications. Adv. Mater. 2024 , 36 , 2405164..

Kumpfer, J. R.; Jin, J.; Rowan, S. J. Stimuli-responsive europium-containing metallo-supramolecular polymers. J. Mater. Chem. 2010 , 20 , 145−151..

Balkenende, D. W. R.; Coulibaly, S.; Balog, S.; Simon, Y. C.; Fiore, G. L.; Weder, C. Mechanochemistry with metallosupramolecular polymers. J. Am. Chem. Soc. 2014 , 136 , 10493−10498..

Li, C. H.; Wang, C.; Keplinger, C.; Zuo, J. L.; Jin, L.; Sun, Y.; Zheng, P.; Cao, Y.; Lissel, F.; Linder, C.; You, X. Z.; Bao, Z. A highly stretchable autonomous self-healing elastomer. Nat. Chem. 2016 , 8 , 618−624..

Hu, J. Y.; Jiao, D.; Hao, X. P.; Kong, X.; Zhang, X. N.; Du, M.; Zheng, Q.; Wu, Z. L. A facile strategy to fabricate tough and adhesive elastomers by in situ formation of coordination complexes as physical crosslinks. Adv. Funct. Mater. 2023 , 33 , 2307402..

Zhang, X.; Tang, Z.; Guo, B.; Zhang, L. Enabling design of advanced elastomer with bioinspired metal–oxygen coordination. ACS Appl. Mater. Interfaces 2016 , 8 , 32520−32527..

Zhu, Y. L.; Zhao, H. Y.; Fu, C. L.; Li, Z. W.; Sun, Z. Y.; Lu, Z. Mechanisms of defect correction by reversible chemistries in covalent organic frameworks. J. Phys. Chem. Lett. 2020 , 11 , 9952−9956..

Zhang, S.; Deng, Y.; Libanori, A.; Zhou, Y.; Yang, J.; Tat, T.; Yang, L.; Sun, W.; Zheng, P.; Zhu, Y. L.; Chen, J.; Tan, S. C. In situ grown silver–polymer framework with coordination complexes for functional artificial tissues. Adv. Mater. 2023 , 35 , 2207916..

Zhu, Y. L.; Liu, H.; Li, Z. W.; Qian, H. J.; Milano, G.; Lu, Z. Y. Galamost: GPU-accelerated large-scale molecular simulation toolkit. J. Comput. Chem. 2013 , 34 , 2197−2211..

He, J.; Tremblay, L.; Lacelle, S.; Zhao, Y. How can photoisomerization of azobenzene induce a large cloud point temperature shift of PNIPAM. Polym. Chem. 2014 , 5 , 5403−5411..

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