Skip to main content
SpringerLink
Log in

Tunable nonlinear optical responses based on host-guest MOF hybrid materials

基于主-客体型金属-有机框架材料的可调谐非线性光学性能

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

Abstract

The realization of tunable nonlinear optical (NLO) responses in a single nano-/micro-structure is extremely important. However, in lack of effective ways to integrate multiple performances, it still faces severe limitations during applications. Herein, we demonstrate a wavelength-dependent NLO micro-structure based on host-guest metal-organic framework (MOF) materials through encapsulating linear dye molecules into periodic one-dimensional (1D) channels. The confinement to non-centrosymmetric polar dye molecules enhances the second-/third-order NLO responses of the hybrid crystals, causing obvious two-photon luminescence (TPL), second harmonic generation (SHG) and third harmonic generation (THG) responses in the as-prepared composites. The highly ordered structures of MOFs impart spatial regulation on the linear dye molecules to realize orientation alignment, resulting in the polarized anisotropy emission. NIR-to-NIR (NIR, near-infrared region) two-photon pumped lasing is realized with the natural whispering gallery mode resonance cavities of MOFs under the excitation of a 1200-nm fs laser. Furthermore, tunable NLO properties such as TPL, SHG and THG are achieved through switching the incident excitation wavelength from 800 to 1500 nm. Such hybrid materials with tunable NLO responses may open a new avenue toward designing multifunctional NLO devices in the future.

摘要

本文通过采用原位自组装工艺将线形有机染料分子组装在 具有一维孔道的金属-有机框架材料(MOFs)中, 成功制备了基于 主-客体系的复合晶态材料. MOFs的高度有序微孔结构赋予线形 染料分子以强烈的限域作用, 促使染料分子一维定向排列, 从而实 现材料的光学性能各向异性. 相比于无限域染料分子, 该复合材料 展示出显著增强的双光子发光性能(TPL), 并利用MOFs单晶晶面 形成的天然谐振腔实现了近红外波段的双光子激光(TPPL). MOFs 孔道中极性染料分子的有序组装使该复合晶体产生二阶/三阶非线 性光学响应, 获得了强的二次谐波(SHG)和三次谐波(THG)效应. 在800–1500 nm范围内调谐激发波长, 该材料展示出激发波长依赖 的非线性光学响应调谐性能, 获得TPL、TPPL、SHG和THG的多 重非线性光学性能. 上述结果为未来设计高效的非线性光学器件 开辟了一条简单有效的途径.

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. Xu J, Li X, Xiong J, et al. Halide perovskites for nonlinear optics. Adv Mater, 2020, 32: 1806736

    Article  CAS  Google Scholar 

  2. Medishetty R, Zaręba JK, Mayer D, et al. Nonlinear optical properties, upconversion and lasing in metal-organic frameworks. Chem Soc Rev, 2017, 46: 4976–5004

    Article  CAS  Google Scholar 

  3. Zheng Q, Zhu H, Chen SC, et al. Frequency-upconverted stimulated emission by simultaneous five-photon absorption. Nat Photon, 2013, 7: 234–239

    Article  CAS  Google Scholar 

  4. Huang J, Guo S, Zhang Z, et al. Designing excellent mid-infrared nonlinear optical materials with fluorooxo-functional group of d0 transition metal oxyfluorides. Sci China Mater, 2019, 62: 1798–1806

    Article  CAS  Google Scholar 

  5. Zheng Z, Li D, Liu Z, et al. Aggregation-induced nonlinear optical effects of AIEgen nanocrystals for ultradeep in vivo bioimaging. Adv Mater, 2019, 31: 1904799

    Article  CAS  Google Scholar 

  6. Aouani H, Rahmani M, Navarro-Cía M, et al. Third-harmonic-upconversion enhancement from a single semiconductor nanoparticle coupled to a plasmonic antenna. Nat Nanotech, 2014, 9: 290–294

    Article  CAS  Google Scholar 

  7. Kharin AY, Lysenko VV, Rogov A, et al. Bi-modal nonlinear optical contrast from Si nanoparticles for cancer theranostics. Adv Opt Mater, 2019, 1801728

  8. Mitetelo N, Venkatakrishnarao D, Ravi J, et al. Chirality-controlled multiphoton luminescence and second-harmonic generation from enantiomeric organic micro-optical waveguides. Adv Opt Mater, 2019, 7: 1801775

    Article  Google Scholar 

  9. Deska R, Sadecka K, Olesiak-Bańska J, et al. Nonlinear plasmonics in eutectic composites: Second harmonic generation and two-photon luminescence in a volumetric Bi2O3-Ag metamaterial. Appl Phys Lett, 2017, 110: 031102

    Article  Google Scholar 

  10. Xiong J, Li X, Yuan C, et al. Wavelength dependent nonlinear optical response of tetraphenylethene aggregation-induced emission luminogens. Mater Chem Front, 2018, 2: 2263–2271

    Article  CAS  Google Scholar 

  11. Kumar KVA, Rao SV, Hamad S, et al. Wavelength dependent nonlinear optical switching in electron beam irradiated CuTTBPc thin film. RSC Adv, 2016, 6: 22083–22089

    Article  CAS  Google Scholar 

  12. Venkatakrishnarao D, Narayana YSLV, Mohaiddon MA, et al. Two-photon luminescence and second-harmonic generation in organic nonlinear surface comprised of self-assembled frustum shaped organic microlasers. Adv Mater, 2017, 29: 1605260

    Article  Google Scholar 

  13. Su J, Zhang J, Tian X, et al. A series of multifunctional coordination polymers based on terpyridine and zinc halide: Second-harmonic generation and two-photon absorption properties and intracellular imaging. J Mater Chem B, 2017, 5: 5458–5463

    Article  CAS  Google Scholar 

  14. He GS, Tan LS, Zheng Q, et al. Multiphoton absorbing materials: Molecular designs, characterizations, and applications. Chem Rev, 2008, 108: 1245–1330

    Article  CAS  Google Scholar 

  15. Kim HS, Lee SM, Ha K, et al. Aligned inclusion of hemicyanine dyes into silica zeolite films for second harmonic generation. J Am Chem Soc, 2004, 126: 673–682

    Article  CAS  Google Scholar 

  16. Pham TCT, Kim HS, Yoon KB. Large increase in the second-order nonlinear optical activity of a hemicyanine-incorporating zeolite film. Angew Chem Int Ed, 2013, 52: 5539–5543

    Article  CAS  Google Scholar 

  17. Zhao D, Timmons DJ, Yuan D, et al. Tuning the topology and functionality of metal-organic frameworks by ligand design. Acc Chem Res, 2011, 44: 123–133

    Article  CAS  Google Scholar 

  18. Jiao L, Wang Y, Jiang HL, et al. Metal-organic frameworks as platforms for catalytic applications. Adv Mater, 2018, 30: 1703663

    Article  Google Scholar 

  19. Niu Z, Cui X, Pham T, et al. A metal-organic framework based methane nano-trap for the capture of coal-mine methane. Angew Chem Int Ed, 2019, 58: 10138–10141

    Article  CAS  Google Scholar 

  20. Nguyen TN, Ebrahim FM, Stylianou KC. Photoluminescent, up-conversion luminescent and nonlinear optical metal-organic frameworks: From fundamental photophysics to potential applications. Coord Chem Rev, 2018, 377: 259–306

    Article  CAS  Google Scholar 

  21. Cui Y, Zhang J, He H, et al. Photonic functional metal-organic frameworks. Chem Soc Rev, 2018, 47: 5740–5785

    Article  CAS  Google Scholar 

  22. Li H, He H, Yu J, et al. Dual-band simultaneous lasing in MOFs single crystals with Fabry-Perot microcavities. Sci China Chem, 2019, 62: 987–993

    Article  CAS  Google Scholar 

  23. Wei Y, Dong H, Wei C, et al. Wavelength-tunable microlasers based on the encapsulation of organic dye in metal-organic frameworks. Adv Mater, 2016, 28: 7424–7429

    Article  CAS  Google Scholar 

  24. Yu J, Cui Y, Xu H, et al. Confinement of pyridinium hemicyanine dye within an anionic metal-organic framework for two-photon-pumped lasing. Nat Commun, 2013, 4: 2719

    Article  Google Scholar 

  25. Venkatakrishnarao D, Mamonov EA, Murzina TV, et al. Advanced organic and polymer whispering-gallery-mode microresonators for enhanced nonlinear optical light. Adv Opt Mater, 2018, 6: 1800343

    Article  Google Scholar 

  26. Yu J, Cui Y, Wu C, et al. Second-order nonlinear optical activity induced by ordered dipolar chromophores confined in the pores of an anionic metal-organic framework. Angew Chem Int Ed, 2012, 51: 10542–10545

    Article  CAS  Google Scholar 

  27. He H, Ma E, Cui Y, et al. Polarized three-photon-pumped laser in a single MOF microcrystal. Nat Commun, 2016, 7: 11087

    Article  CAS  Google Scholar 

  28. Sola-Llano R, Martínez-Martínez V, Fujita Y, et al. Formation of a nonlinear optical host-guest hybrid material by tight confinement of LDS 722 into aluminophosphate 1D nanochannels. Chem Eur J, 2016, 22: 15700–15711

    Article  CAS  Google Scholar 

  29. Kim HS, Pham TT, Yoon KB. Aligned inclusion of dipolar dyes into zeolite channels by inclusion in the excited state. J Am Chem Soc, 2008, 130: 2134–2135

    Article  CAS  Google Scholar 

  30. He H, Zhang X, Yan X, et al. Broadband second harmonic generation in GaAs nanowires by femtosecond laser sources. Appl Phys Lett, 2013, 103: 143110

    Article  Google Scholar 

  31. He H, Ma E, Yu J, et al. Periodically aligned dye molecules integrated in a single MOF microcrystal exhibit single-mode linearly polarized lasing. Adv Opt Mater, 2017, 5: 1601040

    Article  Google Scholar 

  32. Tang B, Sun L, Zheng W, et al. Ultrahigh quality upconverted single-mode lasing in cesium lead bromide spherical microcavity. Adv Opt Mater, 2018, 6: 1800391

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (51632008, U1609219 and 61721005).

Author information

Author notes

  1. These two authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Silicon Materials, Cyrus Tang Center for Sensor Materials and Applications, School of Materials Science and Engineering, Zhejiang University, Hangzhou, 310027, China

    Hongjun Li  (李鸿钧), Lin Zhang  (张琳), Huajun He  (何桦浚), Yu Yang  (杨雨), Yuanjing Cui  (崔元靖) & Guodong Qian  (钱国栋)

Authors
  1. Hongjun Li  (李鸿钧)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lin Zhang  (张琳)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huajun He  (何桦浚)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yu Yang  (杨雨)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yuanjing Cui  (崔元靖)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Guodong Qian  (钱国栋)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Li H and Zhang L designed and performed the experiments, analyzed the data and wrote the paper; He H, Yang Y and Cui Y analyzed the data; Qian G conceived the framework of this paper and revised the paper. All authors contributed to the general discussion.

Corresponding author

Correspondence to Guodong Qian  (钱国栋).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Hongjun Li received his Bachelor’s degree in materials science and engineering from Northeastern University (2017). He is currently pursuing a PhD at the School of Materials Science and Engineering at Zhejiang University under the supervision of Prof. Guodong Qian. His research interest focuses on photonic MOF materials.

Guodong Qian received his Bachelor’s (1988) and Master’s (1992) degrees in materials science from Zhejiang University. He was promoted to Associate Professor, Full Professor, and Cheung Kong Professor in 1999, 2002, and 2011, respectively. His current research interests include hybrid organic-inorganic photonic functional materials and multifunctional porous materials

Supporting Information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, H., Zhang, L., He, H. et al. Tunable nonlinear optical responses based on host-guest MOF hybrid materials. Sci. China Mater. 64, 698–705 (2021). https://doi.org/10.1007/s40843-020-1455-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-020-1455-6

Keywords

Search

Navigation