Skip to main content
SpringerLink
Log in

Axially chiral materials exhibiting blue-emissive ultralong organic phosphorescence and intense circularly polarized luminescence

兼具超长有机磷光和强圆偏振发光性质的蓝光轴手性材料

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

In this work, one type of axially chiral materials with both blue-emissive ultralong organic phosphorescence (UOP) and intense circularly polarized luminescence (CPL) is reported. Such materials not only exhibit extremely small energy gap between the S1 and T1 states (ΔEST, 0.03 eV), greatly promoting the intersystem crossing process for more triplet excitons, but also show ultralong phosphorescent lifetime (5.5 s). As a result, a bright blue afterglow of up to 60 s is achieved in 2-methyltetrahydrofuran at 77 K. The “exciton hourglass” model is further proposed to describe the internal photophysical processes. Moreover, such UOP materials also exhibit intense CPL because of the rigid axially chiral skeleton. Impressively, the luminescence asymmetry factor (glum) value of up to 0.34 can be achieved by applying them as the chiral inducers for liquid crystal materials. This work can provide a guideline and perspective for further designing novel pure organic molecules with both UOP and intense CPL.

摘要

本文报道了一类兼具超长有机磷光(UOP)和强圆偏振发光(CPL)性质的蓝光轴手性材料. 这类材料不仅具有极小的单重态(S1)-三重态(T1)能隙差(ΔEST, 0.03 eV), 能够极大地促进系间窜越过程以产生更多的三重态激子, 而且还具有超长的磷光衰减寿命(5.5 s). 因此, 这类材料在77 K下的2-MeTHF稀溶液中显示长达60 s的亮蓝色余辉. 我们进一步提出了“激子沙漏”模型来描述内部的光物理过程和解释产生超长余辉的原因. 此外, 由于刚性的轴手性骨架, 这类UOP材料还表现出强的CPL活性, 尤其是将它们用作液晶材料的手性诱导剂时, 能够获得0.34的glum值. 本工作对于进一步设计兼具UOP和强CPL性质的新型纯有机分子材料具有重要的指导意义.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Gu L, Shi H, Bian L, et al. Colour-tunable ultra-long organic phosphorescence of a single-component molecular crystal. Nat Photonics, 2019, 13: 406–411

    CAS  Google Scholar 

  2. Zhang G, Palmer GM, Dewhirst MW, et al. A dual-emissive-materials design concept enables tumour hypoxia imaging. Nat Mater, 2009, 8: 747–751

    CAS  Google Scholar 

  3. Kabe R, Notsuka N, Yoshida K, et al. Afterglow organic light-emitting diode. Adv Mater, 2016, 28: 655–660

    CAS  Google Scholar 

  4. Fan Y, Liu S, Wu M, et al. Mobile phone flashlight-excited red afterglow bioimaging. Adv Mater, 2022, 34: 2201280

    CAS  Google Scholar 

  5. Bilen CS, Harrison N, Morantz DJ. Unusual room temperature afterglow in some crystalline organic compounds. Nature, 1978, 271: 235–237

    CAS  Google Scholar 

  6. Ma X, Wang J, Tian H. Assembling-induced emission: An efficient approach for amorphous metal-free organic emitting materials with room-temperature phosphorescence. Acc Chem Res, 2019, 52: 738–748

    CAS  Google Scholar 

  7. Li Q, Li Z. Molecular packing: Another key point for the performance of organic and polymeric optoelectronic materials. Acc Chem Res, 2020, 53: 962–973

    CAS  Google Scholar 

  8. Ma XK, Liu Y. Supramolecular purely organic room-temperature phosphorescence. Acc Chem Res, 2021, 54: 3403–3414

    CAS  Google Scholar 

  9. Guo J, Yang C, Zhao Y. Long-lived organic room-temperature phosphorescence from amorphous polymer systems. Acc Chem Res, 2022, 55: 1160–1170

    CAS  Google Scholar 

  10. Zhang L, Zhao WL, Li M, et al. Recent progress on room-temperature phosphorescent materials of organic small molecules. Acta Chim Sin, 2020, 78: 1030–1040

    CAS  Google Scholar 

  11. An Z, Zheng C, Tao Y, et al. Stabilizing triplet excited states for ultralong organic phosphorescence. Nat Mater, 2015, 14: 685–690

    CAS  Google Scholar 

  12. Chen C, Chi Z, Chong KC, et al. Carbazole isomers induce ultralong organic phosphorescence. Nat Mater, 2021, 20: 175–180

    Google Scholar 

  13. Ye W, Ma H, Shi H, et al. Confining isolated chromophores for highly efficient blue phosphorescence. Nat Mater, 2021, 20: 1539–1544

    CAS  Google Scholar 

  14. Liao Q, Gao Q, Wang J, et al. 9,9-Dimethylxanthene derivatives with room-temperature phosphorescence: Substituent effects and emissive properties. Angew Chem Int Ed, 2020, 59: 9946–9951

    CAS  Google Scholar 

  15. Du J, Poelman D. Identifying near-infrared persistent luminescence in Cr3+-doped magnesium gallogermanates featuring afterglow emission at extremely low temperature. Adv Opt Mater, 2020, 8: 1901848

    CAS  Google Scholar 

  16. Yang X, Zhao L, Chen W, et al. Low-temperature red long-persistent luminescence of Pr3+ doped NaNbO3 with a perovskite structure. J Lumin, 2019, 208: 290–295

    CAS  Google Scholar 

  17. Lojpur V, Nikolić G, Dramićanin MD. Luminescence thermometry below room temperature via up-conversion emission of Y2O3:Yb3+,Er3+ nanophosphors. J Appl Phys, 2014, 115: 203106

    Google Scholar 

  18. Zhu N, Huang Y, Lang L, et al. Low-temperature sintered Pr3+/Er3+ codoped Bi2Mo2O9 microcrystals for multimode optical thermometry and anti-counterfeiting. J Lumin, 2022, 251: 119244

    CAS  Google Scholar 

  19. Lucenti E, Forni A, Botta C, et al. Intrinsic and extrinsic heavy-atom effects on the multifaceted emissive behavior of cyclic triimidazole. Chem Eur J, 2019, 25: 2452–2456

    CAS  Google Scholar 

  20. Yang Z, Xu C, Li W, et al. Boosting the quantum efficiency of ultralong organic phosphorescence up to 52 % via intramolecular halogen bonding. Angew Chem Int Ed, 2020, 59: 17451–17455

    CAS  Google Scholar 

  21. Mao Z, Yang Z, Xu C, et al. Two-photon-excited ultralong organic room temperature phosphorescence by dual-channel triplet harvesting. Chem Sci, 2019, 10: 7352–7357

    CAS  Google Scholar 

  22. Tu D, Cai S, Fernandez C, et al. Boron-cluster-enhanced ultralong organic phosphorescence. Angew Chem Int Ed, 2019, 58: 9129–9133

    CAS  Google Scholar 

  23. Tian S, Ma H, Wang X, et al. Utilizing d−pπ bonds for ultralong organic phosphorescence. Angew Chem Int Ed, 2019, 58: 6645–6649

    CAS  Google Scholar 

  24. Data P, Okazaki M, Minakata S, et al. Thermally activated delayed fluorescence vs. room temperature phosphorescence by conformation control of organic single molecules. J Mater Chem C, 2019, 7: 6616–6621

    CAS  Google Scholar 

  25. Tao Y, Chen R, Li H, et al. Resonance-activated spin-flipping for efficient organic ultralong room-temperature phosphorescence. Adv Mater, 2018, 30: 1803856

    Google Scholar 

  26. Shan H, Liu A, Lv Y, et al. Manipulating the AIE and low-temperature phosphorescence properties of o-carborane-imidazole derivatives via fine tuning their structural features. Dyes Pigments, 2020, 180: 108400

    CAS  Google Scholar 

  27. Zhu H, Badía-Domínguez I, Shi B, et al. Cyclization-promoted ultralong low-temperature phosphorescence via boosting intersystem crossing. J Am Chem Soc, 2021, 143: 2164–2169

    CAS  Google Scholar 

  28. Dhbaibi K, Morgante P, Vanthuyne N, et al. Low-temperature luminescence in organic helicenes: Singlet versus triplet state circularly polarized emission. J Phys Chem Lett, 2023, 14: 1073–1081

    CAS  Google Scholar 

  29. Sang Y, Han J, Zhao T, et al. Circularly polarized luminescence in nanoassemblies: Generation, amplification, and application. Adv Mater, 2020, 32: 1900110

    CAS  Google Scholar 

  30. Parker D, Fradgley JD, Wong KL. The design of responsive luminescent lanthanide probes and sensors. Chem Soc Rev, 2021, 50: 8193–8213

    CAS  Google Scholar 

  31. Yang Y, da Costa RC, Fuchter MJ, et al. Circularly polarized light detection by a chiral organic semiconductor transistor. Nat Photon, 2013, 7: 634–638

    CAS  Google Scholar 

  32. Zhang DW, Li M, Chen CF. Recent advances in circularly polarized electroluminescence based on organic light-emitting diodes. Chem Soc Rev, 2020, 49: 1331–1343

    CAS  Google Scholar 

  33. Li M, Li SH, Zhang D, et al. Stable enantiomers displaying thermally activated delayed fluorescence: Efficient OLEDs with circularly polarized electroluminescence. Angew Chem Int Ed, 2018, 57: 2889–2893

    CAS  Google Scholar 

  34. Zhao WL, Wang YF, Wan SP, et al. Chiral thermally activated delayed fluorescence-active macrocycles displaying efficient circularly polarized electroluminescence. CCS Chem, 2022, 4: 3540–3548

    CAS  Google Scholar 

  35. Hu Y, Huang Z, Willner I, et al. Multicolor circularly polarized luminescence of a single-component system revealing multiple information encryption. CCS Chem, 2023, 1–10

  36. Huang Z, He Z, Ding B, et al. Photoprogrammable circularly polarized phosphorescence switching of chiral helical polyacetylene thin films. Nat Commun, 2022, 13: 7841

    CAS  Google Scholar 

  37. Sun S, Li X, Xu C, et al. Scale effect of circularly polarized luminescent signal of matter. Natl Sci Rev, 2023, 10: nwad072

    Google Scholar 

  38. Xu C, Yin C, Wu W, et al. Tunable room-temperature phosphorescence and circularly polarized luminescence encoding helical supramolecular polymer. Sci China Chem, 2022, 65: 75–81

    CAS  Google Scholar 

  39. Hirata S, Vacha M. Circularly polarized persistent room-temperature phosphorescence from metal-free chiral aromatics in air. J Phys Chem Lett, 2016, 7: 1539–1545

    CAS  Google Scholar 

  40. Liang X, Liu TT, Yan ZP, et al. Organic room-temperature phosphorescence with strong circularly polarized luminescence based on paracyclophanes. Angew Chem Int Ed, 2019, 58: 17220–17225

    CAS  Google Scholar 

  41. Li H, Li H, Wang W, et al. Stimuli-responsive circularly polarized organic ultralong room temperature phosphorescence. Angew Chem Int Ed, 2020, 59: 4756–4762

    CAS  Google Scholar 

  42. Song J, Wang Y, Qu L, et al. Room-temperature phosphorescence of pure axially chiral bicarbazoles. J Phys Chem Lett, 2022, 13: 5838–5844

    CAS  Google Scholar 

  43. Huang W, Fu C, Liang Z, et al. Strong circularly-polarized room-temperature phosphorescence from a feasibly separable scaffold of bidibenzo[b,d]furan with locked axial chirality. Angew Chem Int Ed, 2022, 61: e202202977

    CAS  Google Scholar 

  44. Gu L, Ye W, Liang X, et al. Circularly polarized organic room temperature phosphorescence from amorphous copolymers. J Am Chem Soc, 2021, 143: 18527–18535

    CAS  Google Scholar 

  45. Patil Y, Demangeat C, Favereau L. Recent advances in room temperature phosphorescence of chiral organic materials. Chirality, 2023, 35: 390–410

    CAS  Google Scholar 

  46. Wang X, Ma S, Zhao B, et al. Frontiers in circularly polarized phosphorescent materials. Adv Funct Mater, 2023, 33: 2214364

    CAS  Google Scholar 

  47. Liu R, Ding B, Liu D, et al. Switchable circularly polarized room-temperature phosphorescence based on pure organic amorphous binaphthyl polymer. Chem Eng J, 2021, 421: 129732

    CAS  Google Scholar 

  48. Li M, Wang YF, Zhang D, et al. Axially chiral TADF-active enantiomers designed for efficient blue circularly polarized electroluminescence. Angew Chem Int Ed, 2020, 59: 3500–3504

    CAS  Google Scholar 

  49. Tan KK, Zhang DW, Zhao WL, et al. Axially chiral TADF-active materials with π-extended acceptors for highly efficient circularly polarized electroluminescence. Chem Eng J, 2023, 462: 142123

    CAS  Google Scholar 

  50. Wang Y, Zhang Z, Liu L, et al. Cyanophenylcarbazole isomers exhibiting different UV and visible light excitable room temperature phosphorescence. J Mater Chem C, 2019, 7: 9671–9677

    CAS  Google Scholar 

  51. Zhang DW, Li M, Chen CF. Linear axially chiral conjugated polymers exhibiting ultralong low-temperature phosphorescence and intense circularly polarized luminescence. Angew Chem Int Ed, 2022, 61: e202213130

    CAS  Google Scholar 

  52. Sasikumar D, John AT, Sunny J, et al. Access to the triplet excited states of organic chromophores. Chem Soc Rev, 2020, 49: 6122–6140

    CAS  Google Scholar 

  53. Zhang Y, Su Y, Wu H, et al. Large-area, flexible, transparent, and long-lived polymer-based phosphorescence films. J Am Chem Soc, 2021, 143: 13675–13685

    CAS  Google Scholar 

  54. Uoyama H, Goushi K, Shizu K, et al. Highly efficient organic light-emitting diodes from delayed fluorescence. Nature, 2012, 492: 234–238

    CAS  Google Scholar 

  55. Wang YF, Li M, Zhao WL, et al. An axially chiral thermally activated delayed fluorescent emitter with a dual emitting core for a highly efficient organic light-emitting diode. Chem Commun, 2020, 56: 9380–9383

    CAS  Google Scholar 

  56. Tu ZL, Yan Z, Liang X, et al. Axially chiral biphenyl compound-based thermally activated delayed fluorescent materials for high-performance circularly polarized organic light-emitting diodes. Adv Sci, 2020, 7: 2000804

    CAS  Google Scholar 

  57. Tu ZL, Lu JJ, Luo XF, et al. Blue axially chiral biphenyl based thermally activated delayed fluorescence materials for efficient circularly polarized OLEDs. Adv Opt Mater, 2021, 9: 2100596

    CAS  Google Scholar 

  58. Chen Y, Zhang Y, Li H, et al. Dynamic circularly polarized luminescence with tunable handedness and intensity enabled by achiral dichroic dyes in cholesteric liquid crystal medium. Adv Mater, 2022, 34: 2202309

    CAS  Google Scholar 

  59. Zhang Y, Li H, Geng Z, et al. Inverted circularly polarized luminescence behavior induced by helical nanofibers through chiral co-assembly from achiral liquid crystal polymers and chiral inducers. ACS Nano, 2022, 16: 3173–3181

    CAS  Google Scholar 

  60. Li Y, Yao K, Chen Y, et al. Full-color and white circularly polarized luminescence promoted by liquid crystal self-assembly containing chiral naphthalimide dyes. Adv Opt Mater, 2021, 9: 2100961

    CAS  Google Scholar 

  61. Yoshida S, Morikawa S, Ueda K, et al. Photoinvertible chiral liquid crystal that affords helicity-controlled aromatic conjugated polymers. Adv Opt Mater, 2020, 8: 2000936

    CAS  Google Scholar 

  62. Chen Y, Lu P, Li Z, et al. Dual stimuli-responsive high-efficiency circularly polarized luminescence from light-emitting chiral nematic liquid crystals. ACS Appl Mater Interfaces, 2020, 12: 56604–56614

    CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (92256304 and 22122111), the Ministry of Science and Technology of China (2022YFA1204401), and Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-202105).

Author information

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Molecular Recognition and Function, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Da-Wei Zhang  (张大伟), Meng Li  (李猛) & Chuan-Feng Chen  (陈传峰)

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Da-Wei Zhang  (张大伟), Meng Li  (李猛) & Chuan-Feng Chen  (陈传峰)

Authors
  1. Da-Wei Zhang  (张大伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Meng Li  (李猛)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Chuan-Feng Chen  (陈传峰)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Author contributions Zhang DW, Li M, and Chen CF designed the whole study; Zhang DW synthesized the organic compounds and characterized the properties of compounds; Chen CF proposed the concepts, obtained the funding, managed the projects, and reviewed and edited the initial drafts.

Corresponding author

Correspondence to Chuan-Feng Chen  (陈传峰).

Ethics declarations

Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Da-Wei Zhang received his BS degree from Huazhong University of Science and Technology in 2018. He is currently pursuing a PhD degree at the Institute of Chemistry, Chinese Academy of Sciences under the supervision of Prof. Chuan-Feng Chen. His research direction is the design of chiral TADF and phosphorescence materials and their applications in OLEDs.

Meng Li received his PhD degree from the Institute of Chemistry, Chinese Academy of Sciences in 2015 under the supervision of Prof. Chuan-Feng Chen. He is currently working as an associate professor at the Institute of Chemistry, Chinese Academy of Sciences. His research interests focus on the chiral optoelectronic materials and devices.

Chuan-Feng Chen has been working as a full professor of organic chemistry at the Institute of Chemistry, Chinese Academy of Sciences since 2001. His current research interests include molecular recognition and assembly based on synthetic macrocyclic hosts (pagoda[n]arenes and other macrocyclic arenes), supramolecular luminescent materials, circular polarization luminescent materials, the TADF-based optoelectronic materials and devices, and helicene chemistry.

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Supplementary information

40843_2023_2551_MOESM1_ESM.pdf

Axially chiral materials exhibiting blue-emissive ultralong organic phosphorescence and intense circularly polarized luminescence

Supplementary material, approximately 3.37 MB.

Supplementary material, approximately 2.35 MB.

Supplementary material, approximately 2.05 MB.

Supplementary material, approximately 1.01 MB.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, DW., Li, M. & Chen, CF. Axially chiral materials exhibiting blue-emissive ultralong organic phosphorescence and intense circularly polarized luminescence. Sci. China Mater. 66, 4030–4036 (2023). https://doi.org/10.1007/s40843-023-2551-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-023-2551-y

Keywords

Search

Navigation