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Confining isolated chromophores for highly efficient blue phosphorescence

Nature Materials volume 20, pages 1539–1544 (2021)Cite this article

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Abstract

High-efficiency blue phosphorescence emission is essential for organic optoelectronic applications. However, synthesizing heavy-atom-free organic systems having high triplet energy levels and suppressed non-radiative transitions—key requirements for efficient blue phosphorescence—has proved difficult. Here we demonstrate a simple chemical strategy for achieving high-performance blue phosphors, based on confining isolated chromophores in ionic crystals. Formation of high-density ionic bonds between the cations of ionic crystals and the carboxylic acid groups of the chromophores leads to a segregated molecular arrangement with negligible inter-chromophore interactions. We show that tunable phosphorescence from blue to deep blue with a maximum phosphorescence efficiency of 96.5% can be achieved by varying the charged chromophores and their counterions. Moreover, these phosphorescent materials enable rapid, high-throughput data encryption, fingerprint identification and afterglow display. This work will facilitate the design of high-efficiency blue organic phosphors and extend the domain of organic phosphorescence to new applications.

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Fig. 1: Rational design of high-efficiency blue phosphorescence.
Fig. 2: Photophysical characterizations of TSP crystals under ambient conditions.
Fig. 3: Mechanistic investigations of blue phosphorescence under ambient conditions.
Fig. 4: Photophysical characterizations of TPP, HSM, HPM and TNP crystals under ambient conditions.
Fig. 5: Demonstration of blue phosphorescence for data encryption, fingerprint identification and afterglow display under ambient conditions.

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Data availability

Source data are provided with this paper. The remaining data supporting the findings of this study are available within the paper and its Supplementary Information files and are available from the corresponding authors upon reasonable request.

The X-ray crystallographic coordinates for structures reported in this study have been deposited at the Cambridge Crystallographic Data Centre under deposition numbers 1888289, 1888291–1888293, 2011667–2011675, 2015867 and 2024673. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

This work is supported by the National Key R&D Program of China (2020YFA0709900), the National Natural Science Foundation of China (21875104, 21975120, 51673095, 21973043, 91833304 and 91833302), the Natural Science Fund for Distinguished Young Scholars of Jiangsu Province (BK20180037) and the Postgraduate Research & Practice Innovation Program of Jiangsu Province (KYCX21_1098). We are grateful to the High-Performance Computing Center of Nanjing Tech University for technical support.

Author information

Author notes

  1. These authors contributed equally: Wenpeng Ye, Huili Ma, Huifang Shi.

Authors and Affiliations

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

    Wenpeng Ye, Huili Ma, Huifang Shi, He Wang, Anqi Lv, Lifang Bian, Meng Zhang, Chaoqun Ma, Kun Ling, Mingxing Gu, Yufeng Mao, Xiaokang Yao, Chaofeng Gao, Kang Shen, Wenyong Jia, Jiahuan Zhi, Suzhi Cai, Zhicheng Song, Jingjie Li, Yanyun Zhang, Song Lu, Kun Liu, Chaomin Dong, Qian Wang, Yudong Zhou, Wei Yao, Xiaochun Hang, Zhongfu An & Wei Huang

  2. Department of Materials Chemistry, Huzhou University, Huzhou, China

    Yujian Zhang

  3. State Key Laboratory for Organic Electronics and Information Displays and Institute of Advanced Materials, Nanjing University of Posts and Telecommunications, Nanjing, China

    Hongmei Zhang & Wei Huang

  4. Pharmaceutical, Analytical, and Solid-State Chemistry Research Center, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, Shanghai, China

    Zaiyong Zhang

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

    Xiaogang Liu

  6. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Fuzhou, China

    Xiaogang Liu

  7. Frontiers Science Center for Flexible Electronics, Xi’an Institute of Flexible Electronics and Xi’an Institute of Biomedical Materials and Engineering, Northwestern Polytechnical University, Xi’an, China

    Wei Huang

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  1. Wenpeng Ye
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Contributions

W. Ye, H.S., H.M., Z.A., X.L. and W.H. conceived the experiments and wrote the paper. W. Ye, H.W., L.B., C.M., W.J., J.Z., J.L., Z.S. and X.H. were primarily responsible for the experiments. S.C., S.L., C.D. and H.Z. performed the lifetime measurements. K. Ling, M.Z., W. Yao, Z.Z. and K.S. conducted the single-crystal measurement and analysis. X.Y., Yanyun Zhang, K. Liu and Yujian Zhang measured the quantum efficiency. A.L., M.G. and H.M. contributed to the time-dependent density functional theory calculations. C.G., Y.M. and Y. Zhou programmed the codes for applications. All authors contributed to data analyses.

Corresponding authors

Correspondence to Zhongfu An, Xiaogang Liu or Wei Huang.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Materials thanks Jinsang Kim and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–40, Tables 1–12 and Discussion.

Supplementary Video 1

Blue luminescence and afterglow emission from TSP, TTP, HSM and HPM crystals upon UV excitation.

Supplementary Video 2

A quick response code was printed on a student ID card by inkjet printing, and revealed after removing UV irradiation.

Supplementary Video 3

Afterglow display device, powered by direct current. Numbers gradually disappear within 1 s after the power source is disconnected.

Supplementary Video 4

Afterglow display showing different paths from A to B slowly fading after d.c. excitation.

Supplementary Video 5

Afterglow display used as radar scan operating at various frequencies.

Supplementary Data 1

Crystallographic data for TSP.

Supplementary Data 2

Crystallographic data for DSP.

Supplementary Data 3

Crystallographic data for TPP.

Supplementary Data 4

Crystallographic data for HSM.

Supplementary Data 5

Crystallographic data for HPM.

Supplementary Data 6

Crystallographic data for TNP.

Supplementary Data 7

Crystallographic data for TMP.

Supplementary Data 8

Crystallographic data for diaminopyridine biphenyldicarboxylate (DAB).

Supplementary Data 9

Crystallographic data for diaminopyridine bipyridinedicarboxylate (DAP).

Supplementary Data 10

Crystallographic data for tetrasodium naphthalenetetracarboxylate (TSN).

Supplementary Data 11

Crystallographic data for tetraaminopyridine naphthalenetetracarboxylate (TAN).

Supplementary Data 12

Crystallographic data for tetradimethylaminopyridine naphthalenetetracarboxylate (TDN).

Supplementary Data 13

Crystallographic data for tetraaminopyridine dibromonaphthalenetetracarboxylate (TAB).

Supplementary Data 14

Crystallographic data for tetradimethylaminopyridine dibromonaphthalenetetracarboxylate (TDB)

Supplementary Data 15

Crystallographic data for tetraammonium dibromonaphthalenetetracarboxylate (TNB).

Supplementary Data 16

CheckCIF file for TSP.

Supplementary Data 17

CheckCIF file for DSP.

Supplementary Data 18

CheckCIF file for TPP.

Supplementary Data 19

CheckCIF file for HSM.

Supplementary Data 20

CheckCIF file for HPM.

Supplementary Data 21

CheckCIF file for TNP.

Supplementary Data 22

CheckCIF file for TMP.

Supplementary Data 23

CheckCIF file for DAB.

Supplementary Data 24

CheckCIF file for DAP.

Supplementary Data 25

CheckCIF file for TSN.

Supplementary Data 26

CheckCIF file for TAN.

Supplementary Data 27

CheckCIF file for TDN.

Supplementary Data 28

CheckCIF file for TAB.

Supplementary Data 29

CheckCIF file for TDB.

Supplementary Data 30

CheckCIF file for TNB.

Source data

Source Data Fig. 2

Unprocessed source data used to generate Fig. 2.

Source Data Fig. 3

Unprocessed source data used to generate Fig. 3.

Source Data Fig. 4

Unprocessed source data used to generate Fig. 4.

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Ye, W., Ma, H., Shi, H. et al. Confining isolated chromophores for highly efficient blue phosphorescence. Nat. Mater. 20, 1539–1544 (2021). https://doi.org/10.1038/s41563-021-01073-5

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