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Efficient organic emitters enabled by ultrastrong through-space conjugation

Nature Photonics volume 18, pages 1185–1194 (2024)Cite this article

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Abstract

Manipulating the electronic structure of organic functional materials by through-space conjugation (TSC) to achieve desirable photophysical properties has been a long-standing research focus. Although the working mechanisms of TSC have been demonstrated, the roles that the intrinsic molecular skeleton and extrinsic aggregates play remain unclear. Here four trinaphthylmethanol isomers and four trinaphthylmethane (TNM) isomers with varying connecting sites of naphthalene were synthesized, and their photophysical properties were systematically investigated. The strength of TSC was found to rise from 222-TNM to 111-TNM with the increased number of 1-naphthalene units. In particular, 111-TNM was found to support efficient long-wavelength clusteroluminescence with an absolute quantum yield of 55%. Experimental and theoretical results revealed that the inherent attribute of robust intramolecular interactions within individual molecules is fundamental for ultrastrong TSC, and intermolecular interactions play an auxiliary role in fortifying and stabilizing intramolecular interactions. This work reveals the intrinsic and extrinsic factors for manipulating TSC and provides a reliable strategy for constructing non-conjugated luminogens with efficient clusteroluminescence.

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Fig. 1: Synthesis and single-crystal structures of TNMOH and TNM isomers.
Fig. 2: Photophysical properties of TNMOH isomers.
Fig. 3: Photophysical properties of TNM isomers.
Fig. 4: Single-molecule and crystalline analyses.
Fig. 5: Intermolecular and intramolecular interaction analyses.

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Data availability

The crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre (CCDC) under deposition numbers 2272325 (222-TNMOH), 2272326 (122-TNMOH), 2272327 (112-TNMOH), 2272328 (111-TNMOH), 2272329 (222-TNM), 2272330 (122-TNM), 2272331 (112-TNM) and 2272332 (111-TNM). These data can be obtained free of charge from the CCDC via www.ccdc.cam.ac.uk/data_request/cif. All other data supporting the findings of this study are available within the article and its Supplementary Information, as well as available from the corresponding authors upon reasonable request. Source data are provided with this paper.

References

  1. Ma, S. et al. Organic molecular aggregates: from aggregation structure to emission property. Aggregate 2, e96 (2021).

    Article  Google Scholar 

  2. Fokin, A. A., Gerbig, D. & Schreiner, P. R. σ/σ- and π/π-interactions are equally important: multilayered graphanes. J. Am. Chem. Soc. 133, 20036–20039 (2011).

    Article  Google Scholar 

  3. Ai, X. et al. Efficient radical-based light-emitting diodes with doublet emission. Nature 563, 536–540 (2018).

    Article  ADS  Google Scholar 

  4. Deng, D. et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotechnol. 11, 218–230 (2016).

    Article  ADS  Google Scholar 

  5. Sun, L., Campbell, M. G. & Dinca, M. Electrically conductive porous metal-organic frameworks. Angew. Chem. Int. Ed. 55, 3566–3579 (2016).

    Article  Google Scholar 

  6. Sun, S. et al. 0D perovskites: unique properties, synthesis and their applications. Adv. Sci. 8, e2102689 (2021).

    Article  Google Scholar 

  7. Cai, X.-M. et al. A simple AIE-active salicylideneaniline towards bimodal encryption–decryption with unique ESIPT-inhibited amorphous state. Chem. Eng. J. 466, 143353 (2023).

    Article  Google Scholar 

  8. Li, X. H. & Antonietti, M. Metal nanoparticles at mesoporous N-doped carbons and carbon nitrides: functional Mott–Schottky heterojunctions for catalysis. Chem. Soc. Rev. 42, 6593–6604 (2013).

    Article  Google Scholar 

  9. Yamaguchi, Y., Matsubara, Y., Ochi, T., Wakamiya, T. & Yoshida, Z. How the π conjugation length affects the fluorescence emission efficiency. J. Am. Chem. Soc. 130, 13867–13869 (2008).

    Article  Google Scholar 

  10. Guo, J. et al. Conjugated organic framework with three-dimensionally ordered stable structure and delocalized π clouds. Nat. Commun. 4, 2736 (2013).

    Article  ADS  Google Scholar 

  11. Saal, F. et al. [n]Helicene diimides (n = 5, 6 and 7): through-bond versus through-space conjugation. J. Am. Chem. Soc. 142, 21298–21303 (2020).

  12. Li, J. et al. Achieving multiple quantum-interfered states via through-space and through-bond synergistic effect in foldamer-based single-molecule junctions. J. Am. Chem. Soc. 144, 8073–8083 (2022).

    Article  Google Scholar 

  13. Hoffmann, R. Interaction of orbitals through space and through bonds. Acc. Chem. Res. 4, 1–9 (1971).

    Article  Google Scholar 

  14. Xie, L. S., Skorupskii, G. & Dinca, M. Electrically conductive metal-organic frameworks. Chem. Rev. 120, 8536–8580 (2020).

    Article  Google Scholar 

  15. Fang, F., Jiang, Q. & Klausen, R. S. Poly(cyclosilane) connectivity tunes optical absorbance. J. Am. Chem. Soc. 144, 7834–7843 (2022).

    Article  Google Scholar 

  16. Cai, X. M. et al. Filling the gap between molecular and aggregate states: how does molecular packing affect photophysical properties? Chem. Eng. J. 451, 138627 (2023).

  17. Zhang, J. et al. White-light emission from organic aggregates: a review. Adv. Photonics 4, 014001 (2021).

    Article  ADS  Google Scholar 

  18. Tang, S. et al. Nonconventional luminophores: characteristics, advancements and perspectives. Chem. Soc. Rev. 50, 12616–12655 (2021).

    Article  Google Scholar 

  19. Wang, Y. et al. Sugar-based aggregation-induced emission luminogens: design, structures and applications. Chem. Rev. 120, 4534–4577 (2020).

    Article  Google Scholar 

  20. Li, M., Li, X., An, X., Chen, Z. & Xiao, H. Clustering-triggered emission of carboxymethylated nanocellulose. Front. Chem. 7, 447 (2019).

    Article  ADS  Google Scholar 

  21. Zhang, H. et al. Clusterization-triggered emission: uncommon luminescence from common materials. Mater. Today 32, 275–292 (2020).

    Article  Google Scholar 

  22. Zhang, Z. et al. The role of amide (n,π∗) transitions in polypeptide clusteroluminescence. Cell Rep. Phys. Sci. 3, 100716 (2022).

  23. Zhang, H. & Tang, B. Z. Through-space interactions in clusteroluminescence. JACS Au 1, 1805–1814 (2021).

    Article  Google Scholar 

  24. Zhang, H. et al. Why do simple molecules with ‘isolated’ phenyl rings emit visible light? J. Am. Chem. Soc. 139, 16264–16272 (2017).

    Article  Google Scholar 

  25. Zhang, J. et al. How to manipulate through-space conjugation and clusteroluminescence of simple AIEgens with isolated phenyl rings. J. Am. Chem. Soc. 143, 9565–9574 (2021).

    Article  Google Scholar 

  26. Liu, J. et al. Through-space interaction of tetraphenylethylene: what, where and how. J. Am. Chem. Soc. 144, 7901–7910 (2022).

    Article  Google Scholar 

  27. Xiong, Z. et al. Controllable secondary through-space interaction and clusteroluminescence. CCS Chem. 5, 2832–2844 (2023).

    Article  Google Scholar 

  28. Tu, W. et al. Manipulation of the through‐space interactions in diphenylmethane. Smart Mol. 1, e20220006 (2023).

    Article  Google Scholar 

  29. Chu, B. et al. Aliphatic polyesters with white-light clusteroluminescence. J. Am. Chem. Soc. 144, 15286–15294 (2022).

    Article  Google Scholar 

  30. Chu, B. et al. Altering chain flexibility of aliphatic polyesters for yellow-green clusteroluminescence in 38% quantum yield. Angew. Chem. Int. Ed. 61, e202114117 (2022).

    Article  Google Scholar 

  31. Zhang, Z. et al. Manipulation of clusteroluminescence in carbonyl‐based aliphatic polymers. Aggregate 3, e278 (2022).

    Article  Google Scholar 

  32. Najbar, J. & Turek, A. M. Luminescence of naphthalene in an argon matrix. Geometry changes and multiplet structures. Chem. Phys. Lett. 73, 536–540 (1980).

    Article  ADS  Google Scholar 

  33. Zhang, J. et al. Regulating the proximity effect of heterocycle-containing AIEgens. Nat. Commun. 14, 3772 (2023).

    Article  ADS  Google Scholar 

  34. Tu, Y. et al. An intelligent AIEgen with nonmonotonic multiresponses to multistimuli. Adv. Sci. 7, 2001845 (2020).

    Article  Google Scholar 

  35. Sun, W., Li, M., Fan, J. & Peng, X. Activity-based sensing and theranostic probes based on photoinduced electron transfer. Acc. Chem. Res. 52, 2818–2831 (2019).

    Article  Google Scholar 

  36. Escudero, D. Revising intramolecular photoinduced electron transfer (PET) from first-principles. Acc. Chem. Res. 49, 1816–1824 (2016).

    Article  Google Scholar 

  37. Daly, B., Ling, J. & de Silva, A. P. Current developments in fluorescent PET (photoinduced electron transfer) sensors and switches. Chem. Soc. Rev. 44, 4203–4211 (2015).

    Article  Google Scholar 

  38. Zhang, H. et al. Drawing a clear mechanistic picture for the aggregation-induced emission process. Mater. Chem. Front. 3, 1143–1150 (2019).

    Article  Google Scholar 

  39. Shuai, Z. & Peng, Q. Organic light-emitting diodes: theoretical understanding of highly efficient materials and development of computational methodology. Natl Sci. Rev. 4, 224–239 (2017).

    Article  ADS  Google Scholar 

  40. Spackman, M. A. & Jayatilaka, D. Hirshfeld surface analysis. CrystEngComm 11, 19–32 (2009).

    Article  Google Scholar 

  41. Spackman, P. R. et al. CrystalExplorer: a program for Hirshfeld surface analysis, visualization and quantitative analysis of molecular crystals. J. Appl. Crystallogr. 54, 1006–1011 (2021).

    Article  ADS  Google Scholar 

  42. Sussardi, A. N. et al. Tandem high-pressure crystallography-optical spectroscopy unpacks noncovalent interactions of piezochromic fluorescent molecular rotors. J. Am. Chem. Soc. 145, 19780–19789 (2023).

    Article  Google Scholar 

  43. Huang, H., Yang, L., Facchetti, A. & Marks, T. J. Organic and polymeric semiconductors enhanced by noncovalent conformational locks. Chem. Rev. 117, 10291–10318 (2017).

    Article  Google Scholar 

  44. Huang, H. et al. Combining electron-neutral building blocks with intramolecular ‘conformational locks’ affords stable, high-mobility p- and n-channel polymer semiconductors. J. Am. Chem. Soc. 134, 10966–10973 (2012).

    Article  Google Scholar 

  45. Tirado-Rives, J. & Jorgensen, W. L. Performance of B3LYP density functional methods for a large set of organic molecules. J. Chem. Theory Comput. 4, 297–306 (2008).

    Article  Google Scholar 

  46. Goerigk, L. A comprehensive overview of the DFT-D3 London-dispersion correction. In Non-Covalent Interactions in Quantum Chemistry and Physics: Theory and Applications (eds Otero de la Roza, A. et al.) 195–219 (Elsevier, 2017).

  47. Cukras, J. & Sadlej, J. The influence of the dispersion corrections on the performance of DFT method in modeling HNgY noble gas molecules and their complexes. Chem. Phys. Lett. 691, 319–324 (2018).

    Article  ADS  Google Scholar 

  48. Adamo, C. & Jacquemin, D. The calculations of excited-state properties with time-dependent density functional theory. Chem. Soc. Rev. 42, 845–856 (2013).

    Article  Google Scholar 

  49. Rappé, A. K. et al. APT a next generation QM-based reactive force field model. Mol. Phys. 105, 301–324 (2007).

    Article  ADS  Google Scholar 

  50. Frisch, M. J. et al. Gaussian 16, Revision A.03 (2017).

  51. Shuai, Z. & Peng, Q. Excited states structure and processes: understanding organic light-emitting diodes at the molecular level. Phys. Rep. 537, 123–156 (2014).

    Article  ADS  Google Scholar 

  52. Reimers, J. R. A practical method for the use of curvilinear coordinates in calculations of normal-mode-projected displacements and Duschinsky rotation matrices for large molecules. J. Chem. Phys. 115, 9103–9109 (2001).

    Article  ADS  Google Scholar 

Download references

Acknowledgements

This work is supported by the National Science Foundation of China (grant no. 22205197). J.Z. acknowledges support from the Research Grants Council Postdoctoral Fellowship Scheme of the Hong Kong Special Administrative Region, China (HKUST PDFS2324-6S01). We thank Y. Zhang from the Testing and Analysis Center of the Department of Polymer Science and Engineering at Zhejiang University for assistance in performing the PL spectroscopy measurements. We thank J. Liu from the Testing and Analysis Center of the Department of Chemistry at Zhejiang University for help in performing the X-ray single-crystal diffractometer measurements. We thank the Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates for the help in quantum mechanical calculations.

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Author notes

  1. These authors contributed equally: Qingyang Xu, Jianyu Zhang.

Authors and Affiliations

  1. MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, China

    Qingyang Xu, Jing Zhi Sun, Haoke Zhang & Ben Zhong Tang

  2. Zhejiang-Israel Joint Laboratory of Self-Assembling Functional Materials, ZJU-Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou, China

    Qingyang Xu & Haoke Zhang

  3. Centre of Healthcare Materials, Shaoxing Institute, Zhejiang University, Shaoxing, China

    Qingyang Xu, Jing Zhi Sun & Haoke Zhang

  4. Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology, Hong Kong, China

    Jianyu Zhang & Ben Zhong Tang

  5. School of Science and Engineering, Shenzhen Institute of Aggregate Science and Technology, The Chinese University of Hong Kong, Shenzhen (CUHK-Shenzhen), Guangzhou, China

    Ben Zhong Tang

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Contributions

Q.X. and H.Z. conceived and designed the experiments. Q.X. performed the synthesis and photophysical measurements. J.Z. conducted the theoretical calculations. Q.X., J.Z. and H.Z. analysed the data. Q.X., J.Z., H.Z., J.Z.S. and B.Z.T. took part in the discussion and gave important suggestions. Q.X., J.Z. and H.Z. co-wrote the paper.

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Correspondence to Haoke Zhang or Ben Zhong Tang.

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Nature Photonics thanks Xiaogang Liu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–77 and Tables 1–50.

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Crystallographic data and crystal structures for 222-TNMOH, 122-TNMOH, 112-TNMOH, 111-TNMOH, 222-TNM, 122-TNM, 112-TNM and 111-TNM.

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Xu, Q., Zhang, J., Sun, J.Z. et al. Efficient organic emitters enabled by ultrastrong through-space conjugation. Nat. Photon. 18, 1185–1194 (2024). https://doi.org/10.1038/s41566-024-01527-7

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