New Transparent Rare-Earth-Based Hybrid Glasses: Synthesis, Luminescence, and X-Ray Imaging Application

Abstract

Metal–organic hybrid glasses have recently emerged as the fourth member in the glass family due to its versatile hosting ability to various functional ions. However, no luminescent ions have been successfully introduced into hybrid glasses to date. Here, we reported a benign desolvation method, whereby rare-earth-based hybrid glasses (RE(NO₃)₃(C₅H₂N₄)₂ glasses) were rapidly formed within 1 h at a low temperature down to 140°C. Such a facile synthesis was applicable to the full rare-earth family, including Y, Sc, and lanthanide series. The hybrid glasses exhibited not only a high transparency of over 88% but also a high luminescent quantum yield of up to 70%, which demonstrated a high spatial resolution in X-ray imaging screen. Hydrogen bond played a key role in maintaining the structural integrity of the organic-metal framework, which in turn promoted the radiative recombination of excited states including both singlet and triplet states of organic moiety (4,5-dicyanoiazole, or DCI). An efficient energy transfer from DCI to luminescent lanthanide ions, also known as the antenna effect, was probed by both steady-state and time-resolved spectroscopy. Apart from the luminescent hybrid glasses, the incorporation of inert rare-earth ions such as La, Y, and Lu generated a transparent glass of enhanced room-temperature phosphorescence. This work not only improved the synthesis toolbox of metal–organic hybrid glasses, but also provided an ideal transparent matrix for the energy-transfer investigation between organic linker and rare-earth ions.

Keywords

luminescent glass / multicolor luminescence / rare-earth complexes / ultralong phosphorescence / X-ray imaging

References

[1] a) P. G. Debenedetti and F. H. Stillinger, “Supercooled Liquids and the Glass Transition,” Nature 410 (2001): 259; b) L. L. Beecroft and C. K. Ober, “Nanocomposite Materials for Optical Applications,” Chemistry of Materials 9 (1997): 1302.

[2] D. Möncke, E. I. Kamitsos, D. Palles, et al., “Transition and Post-Transition Metal Ions in Borate Glasses: Borate Ligand Speciation, Cluster Formation, and Their Effect On Glass Transition and Mechanical Properties,” Journal of Chemical Physics 145 (2016): 124501.

[3] C. M. Reddy, B. D. Prasad Raju, N. John Sushma, N. S. Dhoble, and S. J. Dhoble, “A Review on Optical and Photoluminescence Studies of RE³⁺ (RE=Sm, Dy, Eu, Tb and Nd) Ions Doped LCZSFB Glasses,” Renewable & Sustainable Energy Reviews 51 (2015): 566.

[4] A. Ruivo and C. Laia, “CIE Color Coordinates for the Design of Luminescent Glass Materials,” Color Research & Application 49 (2023): 199.

[5] a) R. S. K. Madsen, A. Qiao, J. Sen, et al., “Ultrahigh-Field ⁶⁷Zn NMR Reveals Short-Range Disorder in Zeolitic Imidazolate Framework Glasses,” Science 367 (2020): 1473; b) T. D. Bennett, S. Horike, J. C. Mauro, M. M. Smedskjaer, and L. Wondraczek, “Looking Into the Future of Hybrid Glasses,” Nature Chemistry 16 (2024): 1755.

[6] K. S. Park, Z. Ni, A. P. Côté, et al., “Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks,” Proceedings National Academy of Science United States of America 103 (2006): 10186.

[7] a) T. D. Bennett, J. C. Tan, Y. Yue, et al., “Hybrid Glasses From Strong and Fragile Metal-Organic Framework Liquids,” Nature Communications 6 (2015): 8079; b) W. L. Xue, C. Das, J. B. Weiß, and S. Henke, “Insights Into the Mechanochemical Glass Formation of Zeolitic Imidazolate Frameworks,” Angewandte Chemie International Edition 63 (2024): e202405307.

[8] M. Z. Chen, J. Li, S. Liao, et al., “Multi-Stage Transformations of a Cluster-Based Metal-Organic Framework: Perturbing Crystals to Glass-Forming Liquids That Re-Crystallize at High Temperature,” Angewandte Chemie International Edition 62 (2023): e202305942.

[9] D. Umeyama, S. Horike, M. Inukai, T. Itakura, and S. Kitagawa, “Reversible Solid-to-Liquid Phase Transition of Coordination Polymer Crystals,” Journal of the American Chemical Society 137 (2015): 864.

[10] R. Banerjee, A. Phan, B. Wang, et al., “High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO₂ Capture,” Science 319 (2008): 939.

[11] a) M. A. Ali, W. M. W. Winters, M. A. Mohamed, et al., “Fabrication of Super-Sized Metal Inorganic-Organic Hybrid Glass with Supramolecular Network via Crystallization-Suppressing Approach,” Angewandte Chemie International Edition 62 (2023): e202218094; b) Y. Gong, H. Zhang, P. Li, et al., “Spectral and Temporal Manipulation of Ultralong Phosphorescence Based on Melt-Quenched Glassy Metal–Organic Complexes for Multi-Mode Photonic Functions,” Advanced Functional Materials 34 (2024): 2312491; c) J. Hou, P. Chen, A. Shukla, et al., “Liquid-Phase Sintering of Lead Halide Perovskites and Metal-Organic Framework Glasses,” Science 374 (2021): 621.

[12] B. Zheng, J. Fan, B. Chen, et al., “Rare-Earth Doping in Nanostructured Inorganic Materials,” Chemical Reviews 122 (2022): 5519.

[13] Y. S. Wei, Z. Fan, C. Luo, and S. Horike, “Desolvation of Metal Complexes to Construct Metal-Organic Framework Glasses,” Nature Synthesis 3 (2023): 214.

[14] H. Zhou, C. Xue, P. Weis, et al., “Photoswitching of Glass Transition Temperatures of Azobenzene-Containing Polymers Induces Reversible Solid-to-Liquid Transitions,” Nature Chemistry 9 (2016): 145.

[15] A. M. Abuelela, M. A. Bedair, W. M. Zoghaib, L. D. Wilson, and T. A. Mohamed, “Molecular Structure and Mild Steel/HCl Corrosion Inhibition of 4,5-Dicyanoimidazole: Vibrational, Electrochemical and Quantum Mechanical Calculations,” Journal of Molecular Structure 1230 (2021): 129647.

[16] C. Yuan, W. Fan, P. Zhou, R. Xing, S. Cao, and X. Yan, “High-Entropy Non-Covalent Cyclic Peptide Glass,” Nature Nanotechnology 19 (2024): 1840.

[17] a) Q. Liu, Y. Miao, L. F. Villalobos, et al., “Unit-Cell-thick Zeolitic Imidazolate Framework Films for Membrane Application,” Nature Materials 22 (2023): 1387; b) Y. Jiang, Y. Wang, W. Chen, R. Chen, Y. Li, and C. Li, “Impact of Adsorbed CO on the Conversion of CO2 to Ethylene on 4,5-Dicyanoimidazole Coordinated Cu,” ACS Catalysis 14 (2024): 9870.

[18] a) X. Qiu, X. Yang, Q. Guo, J. Liu, and X. Zhang, “Ln-HOF Nanofiber Organogels With Time-Resolved Luminescence for Programmable and Reliable Encryption,” Nano Letters 23 (2023): 11916; b) X. Lian, R. Chang, G. Huang, et al., “Multicolor Fluorescent Inks Based on Lanthanide Hybrid Organogels for Anticounterfeiting and Logic Circuit Design,” ACS Applied Materials & Interfaces 16 (2024): 6133; c) Y. Yu, Q. Jin, Y. Ren, Y. Wang, D. Zhu, and J. Wang, “Ratiometric Fluorescent Sensor Based On Europium (III)-Functionalized Covalent Organic Framework for Selective and Sensitive Detection of Tetracycline,” Chemical Engineering Journal 465 (2023): 142819; d) Z. Dou, J. Yu, Y. Cui, et al., “Luminescent Metal–Organic Framework Films as Highly Sensitive and Fast-Response Oxygen Sensors,” Journal of the American Chemical Society 136 (2014): 5527.

[19] G. Finkelstein-Zuta, Z. A. Arnon, T. Vijayakanth, et al., “A Self-Healing Multispectral Transparent Adhesive Peptide Glass,” Nature 630 (2024): 368.

[20] a) D. Zhao, Y. Zhu, W. Cheng, et al., “A Dynamic Gel with Reversible and Tunable Topological Networks and Performances,” Matter 2 (2020): 390; b) Y. Xie, X. Zhao, H. Wang, et al., “Hydrogen Bond-Associated Photofluorochromism for Time-Resolved Information Encryption and Anti-Counterfeiting,” Angewandte Chemie International Edition 64 (2024): e202414846.

[21] G. Velazquez, A. Herrera-Gómez, and M. O. Martı́n-Polo, “Identification of Bound Water Through Infrared Spectroscopy in Methylcellulose,” Journal of Food Engineering 59 (2003): 79.

[22] P. Hartmann, R. Jedamzik, S. Reichel, and B. Schreder, “Optical Glass and Glass Ceramic Historical Aspects and Recent Developments: A Schott View,” Applied Optics 49 (2010): D157.

[23] T. T. Li, J. Z. Liu, S. J. Zheng, et al., “Heteronuclear Lanthanide Titanium-Oxygen Cluster Luminescence Thermometer With Adjustable Operating Range and Sensitivity,” Rare Metals (2024), https://doi.org/10.1007/s12598-024-03090-0.

[24] Q. Xu, J. Zhang, J. Z. Sun, H. Zhang, and B. Z. Tang, “Efficient Organic Emitters Enabled by Ultrastrong Through-Space Conjugation,” Nature Photonics 18 (2024): 1185.

[25] L. Li, J. Zhou, J. Han, et al., “Finely Manipulating Room Temperature Phosphorescence by Dynamic Lanthanide Coordination Toward Multi-Level Information Security,” Nature Communications 15 (2024): 3846.

[26] X. Rao, T. Song, J. Gao, et al., “A Highly Sensitive Mixed Lanthanide Metal-Organic Framework Self-Calibrated Luminescent Thermometer,” Journal of the American Chemical Society 135 (2013): 15559.

[27] S. Han, R. Deng, Q. Gu, et al., “Lanthanide-Doped Inorganic Nanoparticles Turn Molecular Triplet Excitons Bright,” Nature 587 (2020): 594.

[28] a) J. X. Wang, L. Gutiérrez-Arzaluz, X. Wang, et al., “Heavy-Atom Engineering of Thermally Activated Delayed Fluorophores for High-Performance X-Ray Imaging Scintillators,” Nature Photonics 16 (2022): 869; b) J. H. Wei, J. B. Luo, Z. L. He, et al., “Phosphonium Iodide Featuring Blue Thermally Activated Delayed Fluorescence for Highly Efficient XRay Scintillator,” Angewandte Chemie International Edition 63 (2024): e202410514.

[29] S. Tobita, M. Arakawa, and I. Tanaka, “The Paramagnetic Metal Effect on the Ligand Localized S1 .Apprx. .Fwdarw. T1 Intersystem Crossing in the Rare-Earth-Metal Complexes With Methyl Salicylate,” Journal of Physical Chemistry 89 (1985): 5649.

[30] W. Ma, Y. Su, Q. Zhang, et al., “Thermally Activated Delayed Fluorescence (TADF) Organic Molecules for Efficient X-Ray Scintillation and Imaging,” Nature Materials 21 (2021): 210.

[31] F. J. Steemers, W. Verboom, D. N. Reinhoudt, E. B. van der Tol, and J. W. Verhoeven, “New Sensitizer-Modified Calix[4]Arenes Enabling Near-UV Excitation of Complexed Luminescent Lanthanide Ions,” Journal of the American Chemical Society 117 (1995): 9408.

[32] M. Latva, H. Takalo, V. M. Mukkala, C. Matachescu, J. C. Rodríguez-Ubis, and J. Kankare, “Correlation Between the Lowest Triplet State Energy Level of the Ligand and Lanthanide(III) Luminescence Quantum Yield,” Journal of Luminescence 75 (1997): 149.

[33] L. Vijayalakshmi, K. N. Kumar, and J. D. Baek, “Cool White Light and Tunable Multicolor Emission From Tb³⁺/Dy³⁺ Co-Activated Glasses Under Different Excitations for WLEDs,” Journal of Rare Earths 42 (2024): 46.

[34] X. Zhang, H. Qiu, W. Luo, et al., “High-Performance X-Ray Imaging Using Lanthanide Metal-Organic Frameworks,” Advanced Science 10 (2023): 2207004.

RIGHTS & PERMISSIONS

2025 The Author(s). Aggregate published by SCUT, AIEI, and John Wiley & Sons Australia, Ltd.