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Original Article Open Access
Water-sensitive multicolor luminescence in lanthanide-organic framework for anti-counterfeiting
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Abstract
The development of high-level anti-counterfeiting techniques is of great significance in economics and security issues. However, intricate reading methods are required to obtain multi-level information stored in different colors, which greatly limits the application of anti-counterfeiting technology on solving real world problems. Herein, we realize multicolor information anti-counterfeiting under simply external stimulation by utilizing the functional groups and multiple emission centers of lanthanide metal organic framework (Ln-MOFs) to tune luminescence color. Water responsive multicolor luminescence represented by both the tunable color from red to blue within the visible region and high sensitive responsivity has been achieved, owing to the increased nonradiative decay pathways and enhanced Eu3+-to-ligand energy back transfer. Remarkably, information hidden in different colors needs to be read with a specific water content, which can be used as an encryption key to ensure the security of the information for high-level anti-counterfeiting. -
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References
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Supplementary Information
Supplementary information for Water-sensitive multicolor luminescence in lanthanide-organic framework for anti-counterfeiting 
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Figure 1.
(a) Structure of 12-connected hexanuclear Eu cluster [Eu6(μ3-OH)8(CO2)12]. Eu, blue; C, black; O, red. (b) Crystal structure of Eu(BDC-NH2) viewed along the a axis. Eu, blue polyhedra; C, gray; O, red; N, blue; H atoms, Me2NH2 cations and free DMF molecules are omitted for clarity. (c) Powder X-ray diffraction patterns of Eu(BDC-NH2), Tb(BDC-NH2) and Gd(BDC-NH2).
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Figure 2.
(a) The concentration of dissolved ligand H2BDC-NH2 in Eu(BDC-NH2) suspension at different time. (b) N2 sorption isotherms of Eu(BDC-NH2) before (red) and after (blue) being treated with water at 77 K. Solid symbols: adsorption, open symbols: desorption.
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Figure 3.
Emission spectra of Eu(BDC-NH2) in the solid state (a) suspended in THF (b) and in water (c) excited at 375 nm.
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Figure 4.
(a) Emission spectra of Eu(BDC-NH2) suspended in THF with different water content excited at 375 nm. (b) Intensities of ligand luminescence and 5D0 → 7F2 transition of Eu(BDC-NH2) in the presence of various content of water. (c) The relationship of luminescence intensity ratio (I430/I614) and water content. (d) Luminescence intensity ratio (I430/I614) measured in THF/H2O mixture with given water content (0.5, 1 and 2 vol%) using different amounts of Eu(BDC-NH2) (0.5, 1.0 and 1.5 mg).
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Figure 5.
(a) CIE chromaticity coordinates of the luminescence color of Eu(BDC-NH2) in THF with different water content (c = 0, 0.01, 0.04, 0.1, 0.3, 0.5, 0.7, 1, 1.5, 2, 3, and 5 vol%, respectively). Photographs of Eu(BDC-NH2) in (b) THF and (c) EtOH with different water content excited at 365 nm.
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Figure 6.
(a) Schematic representation of energy transfer process in Eu(BDC-NH2). (b) Phosphorescence spectra of Gd(BDC-NH2) at 77 K excited at 375 nm in frozen THF and water.
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