Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy

Ting Liu; Zihao Zhu; Shengjie Wang; Li Shen; Alim Abdurahman; Xiaomin Liu; Geyu Lu

doi:10.1038/s41377-025-01993-w

Your Location：

Home >

Browse articles >

Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy

Original Articles

- Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy
- Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy
- Light: Science & Applications 2025年14卷第10期页码：3092-3101
- Affiliations：
  
  1.State Key Laboratory of Integrated Optoelectronics, JLU Region, College of Electronic Science and Engineering, Jilin University, Qianjin Avenue 2699, Changchun 130012, China
  2.College of Chemical Engineering and Environmental Chemistry, Weifang University, Weifang 261061, China
- Author bio：
  
  Alim Abdurahman (alim@jlu.edu.cn)
  Xiaomin Liu (xiaominliu@jlu.edu.cn)
  Geyu Lu (lugy@jlu.edu.cn)
- Funds：
- DOI：10.1038/s41377-025-01993-w
  中图分类号：
- 收稿：2025-05-23，
  
  修回：2025-07-26，
  
  录用：2025-07-27，
  
  网络出版：2025-08-26，
  
  纸质出版：2025-10-31
- Accepted：
Scan QR Code
Ting Liu, Zihao Zhu, Shengjie Wang, 等. Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy[J]. Light: Science & Applications, 2025,14(10):3092-3101.

Liu, T. et al. Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy. Light: Science & Applications, 14, 3092-3101 (2025).
Ting Liu, Zihao Zhu, Shengjie Wang, 等. Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy[J]. Light: Science & Applications, 2025,14(10):3092-3101. DOI： 10.1038/s41377-025-01993-w.

Liu, T. et al. Efficient luminescent stable Chichibabin diradicaloid for near-infrared imaging and photothermal therapy. Light: Science & Applications, 14, 3092-3101 (2025). DOI： 10.1038/s41377-025-01993-w.

摘要

Abstract

Diradicaloids have garnered significant attention due to their unique electronic

photophysical properties and potential applications in functional materials. Characterized by a narrow band gap and near-infrared (NIR) absorption

diradicaloids are promising candidates for NIR-guided photothermal therapy. However

they are often unstable and exhibit non-emissive properties due to high chemical reactivity and very efficient internal conversion. Herein

we report a remarkably stable Chichibabin diradicaloid

TT-CzPh

which exhibits NIR luminescence (λ

= 821 nm) with an efficient photoluminescence quantum yield (PLQY) of 6.4%. Surprisingly

TT-CzPh not only exhibits excellent NIR imaging but also has a very high photothermal conversion efficiency (PCE) of 87.5%. In vivo experim

ents with TT-CzPh nanoparticles demonstrated their effectiveness in tumor photoablation guided by NIR imaging. This work not only advances the development of stable

efficient luminescent Chichibabin’s hydrocarbons but also opens new avenues for bioimaging and cancer phototherapy applications.

关键词

Keywords

references

Wu, J. S. Diradicaloids (Jenny Stanford Publishing, New York, 2022).

Abe, M. Diradicals. Chem. Rev. 113 , 7011–7088 (2013)..

Zeng, Z. B. et al. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals. Chem. Soc. Rev. 44 , 6578–6596 (2015)..

Stuyver, T. et al. Do diradicals behave like radicals? Chem. Rev. 119 , 11291–11351 (2019)..

Rudebusch, G. E. et al. Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals. Nat. Chem. 8 , 753–759 (2016)..

Breher, F. Stretching bonds in main group element compounds-Borderlines between biradicals and closed-shell species. Coord. Chem. Rev. 251 , 1007–1043 (2007)..

Ji, L. et al. Air-stable organic radicals: new-generation materials for flexible electronics? Adv. Mater. 32 , 1908015 (2020)..

Dai, D. C. et al. Spin characteristics in conjugated stable diradicals. Chem. Commun. 60 , 8997–9006 (2024)..

Ishigaki, Y. et al. Carbon-based biradicals: structural and magnetic switching. Chem. Rev. 123 , 13952–13965 (2023)..

Zhu, Y. J. et al. Stable luminescent diradicals: the emergence and potential applications. Angew. Chem. Int. Ed. 64 , e202423470 (2025)..

Abdurahman, A. et al. A highly efficient open-shell singlet luminescent diradical with strong magnetoluminescence properties. Light Sci. Appl. 12 , 272 (2023)..

Matsuoka, R. et al. Single-molecule magnetoluminescence from a spatially confined persistent diradical emitter. J. Am. Chem. Soc. 145 , 13615–13622 (2023)..

Kopp, S. M. et al. Luminescent organic triplet diradicals as optically addressable molecular qubits. J. Am. Chem. Soc. 146 , 27935–27945 (2024)..

Wang, S. J. et al. Spin-state manipulation in a luminescent diradical polymer. Macromolecules 57 , 6133–6139 (2024)..

Hu, X. G. et al. The electronic applications of stable diradicaloids: present and future. J. Mater. Chem. C. 6 , 11232–11242 (2018)..

Tschitschibabin, A. E. Über einige phenylierte derivate des p, p ‐ditolyls. Ber. der Dtsch. Chem. Ges. 40 , 1810–1819 (1907)..

Montgomery, L. K. et al. The molecular structures of Thiele’s and Chichibabin’s hydrocarbons. J. Am. Chem. Soc. 108 , 6004–6011 (1986)..

Zeng, Z. B. et al. Stable tetrabenzo-Chichibabin’s hydrocarbons: tunable ground state and unusual transition between their closed-shell and open-shell resonance forms. J. Am. Chem. Soc. 134 , 14513–14525 (2012)..

Wang, J. et al. Stable oxindolyl-based analogues of Chichibabin’s and Müller’s hydrocarbons. Angew. Chem. Int. Ed. 56 , 14154–14158 (2017)..

Jiang, C. L. et al. Tetrabenzo-Chichibabin’s hydrocarbons: substituent effects and unusual thermochromic and thermomagnetic behaviours. Chem. Commun. 54 , 2389–2392 (2018)..

Majewski, M. A. et al. 5,-10-Dimesityldiindeno-[1,2-a:2′,1′-i ] -phenanthrene: a stable biradicaloid derived from Chichibabin’s hydrocarbon. Chem. Sci. 10 , 3413–3420 (2019)..

Ni, Y. et al. A Chichibabin’s hydrocarbon-based molecular cage: the impact of structural rigid ity on dynamics, stability, and electronic properties. J. Am. Chem. Soc. 142 , 12730–12742 (2020)..

Prajapati, B. et al. An open-shell coronoid with hybrid Chichibabin-Schlenk conjugation. Angew. Chem. Int. Ed. 60 , 22496–22504 (2021)..

Nishiuchi, T. et al. Synthesis of π-Extended Thiele’s and Chichibabin’s hydrocarbons and effect of the π-congestion on conformations and electronic states. J. Am. Chem. Soc. 144 , 7479–7488 (2022)..

Zhou, Z. B.et al. Sulfone-functionalized Chichibabin’s hydrocarbons: stable diradicaloids with symmetry breaking charge transfer contributing to NIR emission beyond 900 nm. J. Am. Chem. Soc. 146 , 6763–6772 (2024)..

Chang, X. M. et al. A stable Chichibabin diradicaloid with near-infrared emission. Angew. Chem. Int. Ed. 63 , e202404853 (2024)..

Zhu, Z. H. et al. Dual channel emissions of Kasha and Anti-Kasha from a single radical molecule. Angew. Chem. Int. Ed. 63 , e202410552 (2024)..

Tan, G. W. & Wang, X. P. Isolable bis(triarylamine) dications: analogues of Thiele’s, Chichibabin’s, and Müller’s hydrocarbons. Acc. Chem. Res. 50 , 1997–2006 (2017)..

Abdurahman, A. & Peng, Q. M. Luminescent radicals—renaissance of an old material. Chin. J. Lumin. 45 , 211–214 (2024)..

Chen, Z. X., Li, Y. & Huang, F. Persistent and stable organic radicals: design, synthesis, and applications. Chem 7 , 288–332 (2021)..

Cui, X. et al. Organic radical materials in biomedical applications: state of the art and perspectives. Exploration 2 , 20210264 (2022)..

Liu, C. H. et al. Thiele’s fluorocarbons: stable diradicaloids with efficient visible-to-near-infrared fluorescence from a zwitterionic excited state. J. Am. Chem. Soc. 145 , 15702–15707 (2023)..

Punzi, A. et al. Dark state of the Thiele hydrocarbon: efficient solvatochromic emission from a nonpolar centrosymmetric singlet diradicaloid. J. Am. Chem. Soc. 145 , 20229–20241 (2023)..

Yu, C. P. et al. Near-infrared luminescent open-shell π-conjugated systems with a bright lowest-energy zwitterionic singlet excited state. Sci. Adv. 10 , eado3476 (2024)..

Zhao, L. L. et al. Stable diradical-derived conjugated radical polymers. Angew. Chem. Int. Ed. 64 , e202507603 (2025)..

Li, H. et al. The role of open-shell organic radical in enhancing anti-tumor photocatalysis reaction of NIR light-activated photosensitizer. Angew. Chem. Int. Ed. 64 , e202423023 (2025)..

Huang, J. X. et al. Solution-processed D-A-π-A-D radicals for highly efficient photothermal conversion. Aggregate 5 , e426 (2024)..

Liang, W. X. et al. Stable open-shell IC-fused fluorenyl enabling efficient photothermal conversion. Sol. RRL 6 , 2200400 (2022)..

Wei, Q. et al. Open-shell poly(3,-4-dioxythiophene) radical for highly efficient photothermal conversion. Adv. Sci. 11 , 2406800 (2024)..

Missaoui, J. & Achour. L. Fundamental characteristics of organic radicals used in biomedical applications. In Organic Radicals (eds Wang, C. Y., Labidi, A. & Lichtfouse, E.) Ch. 4 43–59 (Elsevier, Amsterdam, 2024).

Feng, L. N. et al. Highly stable near-infrared Ⅱ luminescent diradicaloids for cancer phototheranostics. J. Am. Chem. Soc. 146 , 32582–32594 (2024)..

Huang, T. T. et al. Manipulation of intramolecular charge transfer in NIR-Ⅱ emissive organic diradicaloids via a symmetry-breaking design. Chem https://doi.org/10.1016/j.chempr.2025.102621 https://doi.org/10.1016/j.chempr.2025.102621 (2025)..

Chen, D. J. et al. Diradicaloid-loaded polypeptide nanoparticles for two-photon NIR phototheranostics. ACS Appl. Mater. Interfaces 16 , 59907–59920 (2024)..

Turro, N. J. Modern Molecular Photochemistry (University Science Books, Sausalito, 1991).

Smirnov, V. A. & Plotnikov, V. G. The luminescence-spectroscopic properties of aromatic radicals and biradicals. Russian Chem. Rev. 55 , 929–947 (1986)..

Abdurahman, A. et al. A highly stable organic luminescent diradical. Angew. Chem. Int. Ed. 62 , e202300772 (2023)..

Bleaney, B. Anomalous paramagnetism of copper acetate. Rev. Mod. Phys. 25 , 161–162 (1953)..

Lu, T. & Chen, F. W. Multiwfn: a multifunctional wavefunction analyzer. J. Comput. Chem. 33 , 580–592 (2012)..

Liu, Z. Y., Lu, T. & Chen, Q. X. An sp-hybridized all-carboatomic ring, cyclo-[18 ] -carbon: Electronic structure, electronic spectrum, and optical nonlinearity. Carbon 165 , 461–467 (2020)..

Lu, T. A comprehensive electron wavefunction analysis toolbox for chemists, Multiwfn. J. Chem. Phys. 161 , 082503 (2024)..

Jiang, Y. Y. et al. Suppressing electron-phonon coupling in organic photovoltaics for high-efficiency power conversion. Nat. Commun. 14 , 5079 (2023)..

Engelsberg, S. & Schrieffer, J. R. Coupled electron-phonon system. Phys. Rev. 131 , 993–1008 (1963)..

Zhou, J. et al. Hot-band absorption of indocyanine green for advanced anti-stokes fluorescence bioimaging. Light Sci. Appl. 10 , 182 (2021)..

Zhang, Z. et al. Semiconducting polymer nanoparticles in the second near-infrared region for biomedical imagingand therapy. Adv. Opt. Mater. 11 , 2202052 (2023)..

Xie, Z. J. et al. Black phosphorus-based photothermal therapy with aCD47-mediated immune checkpoint blockade for enhanced cancer immunotherapy. Light Sci. Appl. 9 , 161 (2020)..

Qin, Y. et al. Self-assembled metallacage with second near-infrared aggregation-induced emission for enhanced multimodal theranostics. J. Am. Chem. Soc. 144 , 12825–12833 (2022)..

Xiao, P. H. et al. De novo design of reversibly pH-switchable NIR-Ⅱ aggregation-induced emission luminogens for efficient phototheranostics of patient-derived tumor xenografts. J. Am. Chem. Soc. 145 , 334–344 (2023)..

Yan, D. Y. et al. An all-rounder for NIR-Ⅱ phototheranostics: well-tailored 1064 nm-excitable molecule for photothermal combating of orthotopic breast cancer. Angew. Chem. 136 , e202414259 (2024)..

Gao, Y. J. et al. A stable open-shell conjugated diradical polymer with ultra-high photothermal conversion efficiency for NIR-Ⅱ photo-immunotherapy of metastatic tumor. Nanomicro Lett. 16 , 21 (2024)..

You, C. F. et al. The Midas touch by iridium: a second near-infrared aggregation-induced emission-active Metallo-agent for exceptional phototheranostics of breast cancer. J. Am. Chem. Soc. 147 , 2010–2020 (2025)..

Xie, D. L. et al. Organic radiosensitizer with aggregation-induced emission characteristics for tumor ablation through synergistic apoptosis and immunogenic cell death. ACS Nano 19 , 14972–14986 (2025)..

Zhuang, Y. et al. PEGylated cationic liposomes robustly augment vaccine-induced immune responses: role of lymphatic trafficking and biodistribution. J. Control. Release 159 , 135–142 (2012)..

Xiao, J. S. et al. Nanodiamonds-mediated doxorubicin nuclear delivery to inhibit lung metastasis of breast cancer. Biomaterials 34 , 9648–9656 (2013)..

Zhang, X. S. et al. Nanoplaform based on ultra-small Au regulatingphototoxicity and fluorescence off-on function of Ag 2 S for multi-modal diagnosis and treatment of tumor. Chem. Eng. J. 431 , 133212 (2022)..

Liu, S. Y. et al. BOIMPY-based NIR-Ⅱ fluorophore with high bright ness and long absorption beyond 1000 nm for in vivo bioimaging: synergistic steric regulation strategy. ACS Nano 16 , 17424–17434 (2022)..

Yan, J. Q. et al. An autocatalytic multicomponent DNAzyme nanomachine for tumor-specific photothermal therapy sensitization in pancreatic cancer. Nat. Commun. 14 , 6905 (2023)..

Li, L. et al. Chemiluminescent conjugated polymer nanoparticles for deep-tissue inflammation imaging and photodynamic therapy of cancer. J. Am. Chem. Soc. 146 , 5927–5939 (2024)..

Zeng, J. L., Shirihai, O. S. & Grinstaff, M. W. Degradable nanoparticles restore lysosomal pH and autophagic flux in lipotoxic pancreatic beta cells. Adv. Healthc. Mater. 8 , 1801511 (2019)..

Zhou, X. et al. Self-delivery photothermal converter for feedback enhanced tumor therapy by cascade inflammation inhibition. Chem. Eng. J. 453 , 139887 (2023)..

浏览量

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

暂无数据