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

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  • ReceivedJun 17, 2020
  • AcceptedJul 5, 2020
  • PublishedOct 14, 2020



the National Natural Science Foundation of China(51632008,U1609219,61721005)


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

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

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.

Author information

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.

Supplementary data

Supplementary information

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


[1] Xu J, Li X, Xiong J, et al. Halide perovskites for nonlinear optics. Adv Mater, 2020, 321806736 CrossRef PubMed 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, 464976-5004 CrossRef PubMed Google Scholar

[3] Zheng Q, Zhu H, Chen SC, et al. Frequency-upconverted stimulated emission by simultaneous five-photon absorption. Nat Photon, 2013, 7234-239 CrossRef ADS 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, 621798-1806 CrossRef 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, 311904799 CrossRef PubMed 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, 9290-294 CrossRef PubMed ADS 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 CrossRef Google Scholar

[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, 71801775 CrossRef 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, 110031102 CrossRef ADS 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, 22263-2271 CrossRef 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, 622083-22089 CrossRef 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, 291605260 CrossRef PubMed 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, 55458-5463 CrossRef PubMed Google Scholar

[14] He GS, Tan LS, Zheng Q, et al. Multiphoton absorbing materials: Molecular designs, characterizations, and applications. Chem Rev, 2008, 1081245-1330 CrossRef PubMed 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, 126673-682 CrossRef PubMed 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, 525539-5543 CrossRef PubMed 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, 44123-133 CrossRef PubMed Google Scholar

[18] Jiao L, Wang Y, Jiang HL, et al. Metal-organic frameworks as platforms for catalytic applications. Adv Mater, 2018, 301703663 CrossRef PubMed 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, 5810138-10141 CrossRef PubMed Google Scholar

[20] Nguyen TN, Ebrahim FM, Stylianou KC. Photoluminescent, upconversion luminescent and nonlinear optical metal-organic frameworks: From fundamental photophysics to potential applications. Coord Chem Rev, 2018, 377259-306 CrossRef Google Scholar

[21] Cui Y, Zhang J, He H, et al. Photonic functional metal-organic frameworks. Chem Soc Rev, 2018, 475740-5785 CrossRef PubMed 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, 62987-993 CrossRef 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, 287424-7429 CrossRef PubMed 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, 42719 CrossRef PubMed ADS 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, 61800343 CrossRef 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, 5110542-10545 CrossRef PubMed Google Scholar

[27] He H, Ma E, Cui Y, et al. Polarized three-photon-pumped laser in a single MOF microcrystal. Nat Commun, 2016, 711087 CrossRef PubMed ADS 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, 2215700-15711 CrossRef PubMed 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, 1302134-2135 CrossRef PubMed 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, 103143110 CrossRef ADS 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, 51601040 CrossRef 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, 61800391 CrossRef Google Scholar

  • Figure 1

    (a) Schematic diagram of synthesizing ZJU-68 and LDS-722@ZJU-68 hybrid microcrystals. (b) The corresponding powder XRD patterns of ZJU-68 and dye-assembled ZJU-68 microcrystals.

  • Figure 2

    (a) TPL emission spectra of LDS-722 and LDS-722@ZJU-68 excited at 1020 nm. (b) SHG spectra of ZJU-68, KDP, and LDS-722@ZJU-68 crystals excited at 1020 nm.

  • Figure 3

    (a) The emission spectra which were analyzed under four different excitation polarizations (θ = 0°–90°), excited at 1200 nm. Inset: schematic diagram of the measurement geometry for an individual crystal. (b) TPL and (c) SHG intensity plotted against polarization direction of incident light in LDS-722@ZJU-68 at 1200 nm (5.22 mJ cm−2) from 0° to 360°. The red and blue lines indicate the cos2θ and cos4θ fits for TPL and SHG, respectively.

  • Figure 4

    (a) 800 nm pumped emission spectra of LDS-722@ZJU-68. Insets: the micrograph of LDS-722@ZJU-68 crystal excited at 800 nm (left) and log-log plots for the SHG intensity vs. the excitation energy density, showing a slope of ∼ 2.02 (right). (b) 1000 nm pumped emission spectra of LDS-722@ZJU-68. Insets: the micrograph of LDS-722@ZJU-68 crystal excited at 1000 nm (left) and log-log plots for the SHG and TPL intensities vs. the excitation energy densities, showing the slopes of ∼ 2.25 and 1.89, respectively (right). (c) 1200 nm pumped emission spectra of LDS-722@ZJU-68. Insets: the micrograph of LDS-722@ZJU-68 crystal excited at 1200 nm (left) and log-log plots for the SHG intensity vs. the excitation energy density, showing the slope of ∼ 1.92 (top right) and two-photon emission intensity as a function of pump energy showing the lasing threshold at ∼7.74 mJ cm−2 and the FWHM showing a dramatical decrease from ∼ 67 to ∼ 0.9 nm (bottom right). (d) 1400 nm pumped emission spectra of LDS-722@ZJU-68. Insets: the micrograph of LDS-722@ZJU-68 crystal excited at 1400 nm (left) and log-log plots for the SHG and THG intensities vs. the excitation energy densities with the slopes of ∼ 1.94 and 2.90, respectively (right). Scale bars: 15 μm.


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