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Colour-tunable ultra-long organic phosphorescence of a single-component molecular crystal

Nature Photonics volume 13, pages 406–411 (2019)Cite this article

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Abstract

Materials exhibiting long-lived, persistent luminescence in the visible spectrum are useful for applications in the display, information encryption and bioimaging sectors1,2,3,4. Herein, we report the development of several organic phosphors that provide colour-tunable, ultra-long organic phosphorescence (UOP). The emission colour can be tuned by varying the excitation wavelength, allowing dynamic colour tuning from the violet to the green part of the visible spectrum. Our experimental data reveal that these organic phosphors can have an ultra-long lifetime of 2.45 s and a maximum phosphorescence efficiency of 31.2%. Furthermore, we demonstrate the applications of colour-tunable UOP for use in a multicolour display and visual sensing of ultraviolet light in the range from 300 to 360 nm. The findings open the opportunity for the development of smart luminescent materials and sensors with dynamically controlled phosphorescence.

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Fig. 1: Schematic representation for the manipulation of colour-tunable UOP.
Fig. 2: Photoluminescence characterization of TMOT crystalline powder under ambient conditions.
Fig. 3: Mechanistic investigation of colour-tunable UOP in single-component crystals under ambient conditions.
Fig. 4: Phosphorescence properties and crystal structures of DMOT and CYAD crystalline powder under ambient conditions.
Fig. 5: Demonstration of colour-tunable UOP for multicolour display and visual detection of ultraviolet light under ambient conditions.

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Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.

References

  1. Pan, Z., Lu, Y. & Liu, F. Sunlight-activated long-persistent luminescence in the near-infrared from Cr3+-doped zinc gallogermanates. Nat. Mater. 11, 58–63 (2012).

    Article  ADS  Google Scholar 

  2. Maldiney, T. et al. The in vivo activation of persistent nanophosphors for optical imaging of vascularization, tumours and grafted cells. Nat. Mater. 13, 418–426 (2014).

    Article  ADS  Google Scholar 

  3. Xu, S., Chen, R., Zheng, C. & Huang, W. Excited state modulation for organic afterglow: materials and applications. Adv. Mater. 28, 9920–9940 (2016).

    Article  Google Scholar 

  4. Su, Y. et al. Ultralong room temperature phosphorescence from amorphous organic materials toward confidential information encryption and decryption. Sci. Adv. 4, 9732–9743 (2018).

    Article  Google Scholar 

  5. Lee, J. et al. Universal process-inert encoding architecture for polymer microparticles. Nat. Mater. 13, 524–529 (2014).

    Article  ADS  Google Scholar 

  6. Lee, H., Kim, J., Kim, H., Kim, J. & Kwon, S. Colour-barcoded magnetic microparticles for multiplexed bioassays. Nat. Mater. 9, 745–749 (2010).

    Article  ADS  Google Scholar 

  7. Deng, R. et al. Temporal full-colour tuning through non-steady-state upconversion. Nat. Nanotechnol. 10, 237–242 (2015).

    Article  ADS  Google Scholar 

  8. Pan, L. et al. Truly fluorescent excitation-dependent carbon dots and their applications in multicolor cellular imaging and multidimensional sensing. Adv. Mater. 27, 7782–7787 (2015).

    Article  Google Scholar 

  9. Farinola, G. M. & Ragni, R. Electroluminescent materials for white organic light emitting diodes. Chem. Soc. Rev. 40, 3467–3482 (2011).

    Article  Google Scholar 

  10. Irie, M., Fukaminato, T., Matsuda, K. & Kobatake, E. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem. Rev. 114, 12174–12277 (2014).

    Article  Google Scholar 

  11. Mao, Z. et al. Linearly tunable emission colors obtained from a fluorescent–phosphorescent dual-emission compound by mechanical stimuli. Angew. Chem. Int. Ed. 54, 6270–6273 (2015).

    Article  Google Scholar 

  12. Sun, Y. et al. Quantum-sized carbon dots for bright and colorful photoluminescence. J. Am. Chem. Soc. 128, 7756–7757 (2006).

    Article  Google Scholar 

  13. Chen, O. et al. Excitation-intensity-dependent color-tunable dual emissions from manganese-doped CdS/ZnS core/shell nanocrystals. Angew. Chem. Int. Ed. 49, 10132–10135 (2010).

    Article  Google Scholar 

  14. Lee, K. et al. Excitation-dependent visible fluorescence in decameric nanoparticles with monoacylglycerol cluster chromophores. Nat. Commun. 4, 1544–1551 (2013).

    Article  Google Scholar 

  15. Xu, J. & Tanabe, S. Persistent luminescence instead of phosphorescence: History, mechanism, and perspective. J. Lumin. 205, 581–620 (2019).

    Article  Google Scholar 

  16. Bolton, O., Lee, K., Kim, H., Lin, K. Y. & Kim, J. Activating efficient phosphorescence from purely organic materials by crystal design. Nat. Chem. 3, 205–210 (2011).

    Article  Google Scholar 

  17. Zhang, G. et al. Multi-emissive difluoroboron dibenzoylmethane polylactide exhibiting intense fluorescence and oxygen-sensitive room-temperature phosphorescence. J. Am. Chem. Soc. 129, 8942–8943 (2007).

    Article  Google Scholar 

  18. Yang, Z. et al. Intermolecular electronic coupling of organic units for efficient persistent room-temperature phosphorescence. Angew. Chem. Int. Ed. 55, 2181–2185 (2016).

    Article  Google Scholar 

  19. He, Z. et al. White light emission from a single organic molecule with dual phosphorescence at room temperature. Nat. Commun. 8, 416 (2017).

    Article  ADS  Google Scholar 

  20. Xie, Y. et al. How the molecular packing affects the room temperature phosphorescence in pure organic compounds: ingenious molecular design, detailed crystal analysis, and rational theoretical calculations. Adv. Mater. 29, 1606829–1606836 (2017).

    Article  Google Scholar 

  21. Shoji, Y. et al. Unveiling a new aspect of simple arylboronic esters: long-lived room-temperature phosphorescence from heavy-atom-free molecules. J. Am. Chem. Soc. 139, 2728–2733 (2017).

    Article  Google Scholar 

  22. Wei, J. et al. Induction of strong long-lived room-temperature phosphorescence of N-phenyl-2-naphthylamine molecules by confinement in a crystalline dibromobiphenyl matrix. Angew. Chem. Int. Ed. 55, 15589–15593 (2016).

    Article  Google Scholar 

  23. Hirata, S. et al. Efficient persistent room temperature phosphorescence in organic amorphous materials under ambient conditions. Adv. Funct. Mater. 23, 3386–3397 (2013).

    Article  Google Scholar 

  24. Yang, X. & Yan, D. Strongly enhanced long-lived persistent room temperature phosphorescence based on the formation of metal–organic hybrids. Adv. Opt. Mater. 4, 897–905 (2016).

    Article  Google Scholar 

  25. An, Z. et al. Stabilizing triplet excited states for ultralong organic phosphorescence. Nat. Mater. 14, 685–690 (2015).

    Article  ADS  Google Scholar 

  26. Lucenti, E. et al. Cyclic triimidazole derivatives: intriguing examples of multiple emissions and ultralong phosphorescence at room temperature. Angew. Chem. Int. Ed. 56, 16302–16307 (2017).

    Article  Google Scholar 

  27. Ma, X., Xu, C., Wang, J. & Tian, H. Heavy-atom-free amorphous pure organic polymers with efficient room-temperature phosphorescence emission. Angew. Chem. Int. Ed. 130, 11020–11024 (2018).

    Article  Google Scholar 

  28. Li, Q. et al. Induction of long-lived room temperature phosphorescence of carbon dots by water in hydrogen-bonded matrices. Nat. Commun. 9, 734 (2018).

    Article  ADS  Google Scholar 

  29. Dou, X. et al. Clustering-triggered emission and persistent room temperature phosphorescence of sodium alginate. Biomacromolecules 19, 2014–2022 (2018).

    Article  Google Scholar 

  30. Ogoshi, T. et al. Ultralong room-temperature phosphorescence from amorphous polymer poly(styrene sulfonic acid) in air in the dry solid state. Adv. Funct. Mater. 28, 1707369–1707376 (2018).

    Article  Google Scholar 

  31. Tao, S. et al. Design of metal-free polymer carbon dots: a new class of room temperature phosphorescent materials. Angew. Chem. Int. Ed. 57, 2393–2398 (2018).

    Article  Google Scholar 

  32. Kim, T. et al. Full-colour quantum dot displays fabricated by transfer printing. Nat. Photon. 5, 176–182 (2011).

    Article  ADS  Google Scholar 

  33. Baryshnikov, G., Minaev, B. & Ågren, H. Theory and calculation of the phosphorescence phenomenon. Chem. Rev. 117, 6500–6537 (2017).

    Article  Google Scholar 

Download references

Acknowledgements

This work is supported by the National Natural Science Foundation of China (21875104, 51673095, 91833304, 91833302 and 61605074), National Basic Research Program of China (973 Program, No. 2015CB932200), Natural Science Fund for Distinguished Young Scholars of Jiangsu Province (BK20180037), the Natural Science Fund for Colleges and Universities (17KJB430020) of Jiangsu Province, and Nanjing Tech Start-up Grant (3983500158 and 3983500169). We are grateful to the High Performance Computing Center of Nanjing Tech University for technical support.

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  1. These authors contributed equally: Long Gu, Huifang Shi.

Authors and Affiliations

  1. Key Laboratory of Flexible Electronics & Institute of Advanced Materials, Nanjing Tech University, Nanjing, China

    Long Gu, Huifang Shi, Lifang Bian, Mingxing Gu, Kun Ling, Xuan Wang, Huili Ma, Suzhi Cai, Weihua Ning, Lishun Fu, He Wang, Shan Wang, Yaru Gao, Wei Yao, Fengwei Huo, Youtian Tao, Zhongfu An & Wei Huang

  2. Department of Chemistry, National University of Singapore, Singapore, Singapore

    Xiaogang Liu

  3. Institute of Flexible Electronics, Northwestern Polytechnical University, Xi’an, China

    Wei Huang

  4. Key Laboratory for Organic Electronics and Information Displays & Jiangsu Key Laboratory for Biosensors, Institute of Advanced Materials, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing, China

    Wei Huang

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Contributions

L.G., H.S., Z.A., X.L. and W.H. conceived the experiments. H.S., Z.A., X.L. and W.H. wrote the manuscript. L.G., H.S., L.B., M.G., S.W., Y.G., W.Y. and F.H. were primarily responsible for the experiments. K.L. and L.F. measured the quantum efficiency. X.W., S.W. and H.W. performed the lifetime measurements. S.C., W.N. and Y.T. conducted the single-crystal measurement and analysis. H.M. contributed to TD-DFT calculations. All authors contributed to the data analyses.

Corresponding authors

Correspondence to Zhongfu An, Xiaogang Liu or Wei Huang.

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Supplementary information

Supplementary Information

Additional photophysical properties and theoretical calculations.

Supplementary Video 1

Demonstration of colour switching of the emission from the TMOT compound.

Supplementary Video 2

Visible blue phosphorescence from the TMOT compound.

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Gu, L., Shi, H., Bian, L. et al. Colour-tunable ultra-long organic phosphorescence of a single-component molecular crystal. Nat. Photonics 13, 406–411 (2019). https://doi.org/10.1038/s41566-019-0408-4

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