Lanthanide-doped metal-organic frameworks with multicolor mechanoluminescence

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  • ReceivedJul 18, 2020
  • AcceptedAug 24, 2020
  • PublishedDec 15, 2020


Funded by

the National Natural Science Foundation of China(51832005)


This work was supported by the National Natural Science Foundation of China (51832005). The authors also thank Dr. Pengfei Liu and Weibin Ye for their help in DFT calculation and CL characterizations, respectively.

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Xie RJ, Zhuang Y and Chen W conceived and designed the project, wrote and revised the paper; Chen W was primarily responsible for the experiments; Lv Y, Chen C and Wang MS helped revise this article, perform ML measurements and CL characterizations, respectively. All authors contributed to the general discussion.

Author information

Wenwei Chen is currently a PhD student at the College of Materials, Xiamen University. He completed his master degree in 2016 from Xiamen University. His current research focuses on luminescent MOF materials.

Rong-Jun Xie received his master degree in 1995 from Xi’an Jiaotong University, and received his PhD degree in 1998 from Shanghai Institute of Ceramics, Chinese Academy of Sciences. He is now a professor in the College of Materials, Xiamen University. His current research focuses on the application of rare earth doped luminescent materials and semiconductor lighting devices.


Supplementary information

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


[1] Li H, Eddaoudi M, O'Keeffe M, et al. Design and synthesis of an exceptionally stable and highly porous metal-organic framework. Nature, 1999, 402: 276-279 CrossRef ADS Google Scholar

[2] Eddaoudi M, Kim J, Rosi N, et al. Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage. Science, 2002, 295: 469-472 CrossRef PubMed ADS Google Scholar

[3] Yaghi OM, O’Keeffe M, Ockwig NW, et al. Reticular synthesis and the design of new materials. Nature, 2003, 423: 705-714 CrossRef PubMed Google Scholar

[4] Furukawa H, Cordova KE, O'Keeffe M, et al. The chemistry and applications of metal-organic frameworks. Science, 2013, 341: 1230444 CrossRef PubMed Google Scholar

[5] Rowsell JLC, Spencer EC, Eckert J, et al. Gas adsorption sites in a large-pore metal-organic framework. Science, 2005, 309: 1350-1354 CrossRef PubMed ADS Google Scholar

[6] Kim H, Yang S, Rao SR, et al. Water harvesting from air with metal-organic frameworks powered by natural sunlight. Science, 2017, 356: 430-434 CrossRef PubMed ADS Google Scholar

[7] Rosi NL, Eckert J, Eddaoudi M, et al. Hydrogen storage in microporous metal-organic frameworks. Science, 2003, 300: 1127-1129 CrossRef PubMed ADS Google Scholar

[8] Liang Z, Qu C, Guo W, et al. Pristine metal-organic frameworks and their composites for energy storage and conversion. Adv Mater, 2018, 30: 1702891 CrossRef PubMed Google Scholar

[9] Lee JY, Farha OK, Roberts J, et al. Metal-organic framework materials as catalysts. Chem Soc Rev, 2009, 38: 1450-1459 CrossRef PubMed Google Scholar

[10] Wu MX, Yang YW. Metal-organic framework (MOF)-based drug/cargo delivery and cancer therapy. Adv Mater, 2017, 29: 1606134 CrossRef PubMed Google Scholar

[11] Kreno LE, Leong K, Farha OK, et al. Metal-organic framework materials as chemical sensors. Chem Rev, 2012, 112: 1105-1125 CrossRef PubMed Google Scholar

[12] Zhang T, Lin W. Metal-organic frameworks for artificial photosynthesis and photocatalysis. Chem Soc Rev, 2014, 43: 5982-5993 CrossRef PubMed Google Scholar

[13] Fang X, Shang Q, Wang Y, et al. Single Pt atoms confined into a metal-organic framework for efficient photocatalysis. Adv Mater, 2018, 30: 1705112 CrossRef PubMed Google Scholar

[14] Yan B. Lanthanide-functionalized metal-organic framework hybrid systems to create multiple luminescent centers for chemical sensing. Acc Chem Res, 2017, 50: 2789-2798 CrossRef PubMed Google Scholar

[15] Rao X, Song T, Gao J, et al. A highly sensitive mixed lanthanide metal-organic framework self-calibrated luminescent thermometer. J Am Chem Soc, 2013, 135: 15559-15564 CrossRef PubMed Google Scholar

[16] Cui Y, Song R, Yu J, et al. Dual-emitting MOF⊃dye composite for ratiometric temperature sensing. Adv Mater, 2015, 27: 1420-1425 CrossRef PubMed Google Scholar

[17] Cui Y, Xu H, Yue Y, et al. A luminescent mixed-lanthanide metal-organic framework thermometer. J Am Chem Soc, 2012, 134: 3979-3982 CrossRef PubMed Google Scholar

[18] Cui Y, Zhu F, Chen B, et al. Metal–organic frameworks for luminescence thermometry. Chem Commun, 2015, 51: 7420-7431 CrossRef PubMed Google Scholar

[19] Liu J, Zhuang Y, Wang L, et al. Achieving multicolor long-lived luminescence in dye-encapsulated metal-organic frameworks and its application to anticounterfeiting stamps. ACS Appl Mater Interfaces, 2018, 10: 1802-1809 CrossRef PubMed Google Scholar

[20] Li Z, Wang G, Ye Y, et al. Loading photochromic molecules into a luminescent metal-organic framework for information anticounterfeiting. Angew Chem Int Ed, 2019, 58: 18025-18031 CrossRef PubMed Google Scholar

[21] 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 CrossRef PubMed ADS Google Scholar

[22] He H, Ma E, Cui Y, et al. Polarized three-photon-pumped laser in a single MOF microcrystal. Nat Commun, 2016, 7: 11087 CrossRef PubMed ADS 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 CrossRef PubMed Google Scholar

[24] Medishetty R, Nalla V, Nemec L, et al. A new class of lasing materials: Intrinsic stimulated emission from nonlinear optically active metal-organic frameworks. Adv Mater, 2017, 29: 1605637 CrossRef PubMed Google Scholar

[25] Wen Y, Sheng T, Zhu X, et al. Introduction of red-green-blue fluorescent dyes into a metal-organic framework for tunable white light emission. Adv Mater, 2017, 29: 1700778 CrossRef PubMed Google Scholar

[26] Chen W, Zhuang Y, Wang L, et al. Color-tunable and high-efficiency dye-encapsulated metal–organic framework composites used for smart white-light-emitting diodes. ACS Appl Mater Interfaces, 2018, 10: 18910-18917 CrossRef PubMed Google Scholar

[27] Wang Z, Zhu CY, Mo JT, et al. White-light emission from dual-way photon energy conversion in a dye-encapsulated metal-organic framework. Angew Chem Int Ed, 2019, 58: 9752-9757 CrossRef PubMed Google Scholar

[28] Yuan L, Yin M, Yuan E, et al. Syntheses, structures and luminescence of europium α-thiophene carboxylates coordination polymer and supramolecular compound. Inorg Chim Acta, 2004, 357: 89-94 CrossRef Google Scholar

[29] Eliseeva SV, Pleshkov DN, Lyssenko KA, et al. Highly luminescent and triboluminescent coordination polymers assembled from lanthanide β-diketonates and aromatic bidentate O-donor ligands. Inorg Chem, 2010, 49: 9300-9311 CrossRef PubMed Google Scholar

[30] Hasegawa Y, Hieda R, Miyata K, et al. Brilliant triboluminescence of a lanthanide coordination polymer with low-vibrational-frequency and non-centrosymmetric structural networks. Eur J Inorg Chem, 2011, 2011(32): 4978-4984 CrossRef Google Scholar

[31] Hasegawa Y, Tateno S, Yamamoto M, et al. Effective photo- and triboluminescent europium(III) coordination polymers with rigid triangular spacer ligands. Chem Eur J, 2017, 23: 2666-2672 CrossRef PubMed Google Scholar

[32] Hirai Y, Nakanishi T, Kitagawa Y, et al. Triboluminescence of lanthanide coordination polymers with face-to-face arranged substituents. Angew Chem Int Ed, 2017, 56: 7171-7175 CrossRef PubMed Google Scholar

[33] Bacon F. The advancement of learning [1605]. In: Devey J (ed). Fourth Book, Chapter III. New York: P.F. Collier and Son, 1901. Google Scholar

[34] Herschel AS. Triboluminescence. Nature, 1899, 60: 29 CrossRef ADS Google Scholar

[35] Sage I, Bourhill G. Triboluminescent materials for structural damage monitoring. J Mater Chem, 2001, 11: 231-245 CrossRef Google Scholar

[36] Wang X, Zhang H, Yu R, et al. Dynamic pressure mapping of personalized handwriting by a flexible sensor matrix based on the mechanoluminescence process. Adv Mater, 2015, 27: 2324-2331 CrossRef PubMed Google Scholar

[37] Peng D, Chen B, Wang F. Recent advances in doped mechanoluminescent phosphors. ChemPlusChem, 2015, 80: 1209-1215 CrossRef PubMed Google Scholar

[38] Tu D, Xu CN, Yoshida A, et al. LiNbO3:Pr3+: A multipiezo material with simultaneous piezoelectricity and sensitive piezoluminescence. Adv Mater, 2017, 29: 1606914 CrossRef PubMed Google Scholar

[39] Du Y, Jiang Y, Sun T, et al. Mechanically excited multicolor luminescence in lanthanide ions. Adv Mater, 2019, 31: 1807062 CrossRef PubMed Google Scholar

[40] Liu L, Xu CN, Yoshida A, et al. Scalable elasticoluminescent strain sensor for precise dynamic stress imaging and onsite infrastructure diagnosis. Adv Mater Technol, 2019, 4: 1800336 CrossRef Google Scholar

[41] Chen C, Zhuang Y, Tu D, et al. Creating visible-to-near-infrared mechanoluminescence in mixed-anion compounds SrZn2S2O and SrZnSO. Nano Energy, 2020, 68: 104329 CrossRef Google Scholar

[42] Chandra BP, Rathore AS. Classification of mechanoluminescence. Cryst Res Technol, 1995, 30: 885-896 CrossRef Google Scholar

[43] Chandra BP, Chandra VK, Jha P. Models for intrinsic and extrinsic fracto-mechanoluminescence of solids. J Lumin, 2013, 135: 139-153 CrossRef ADS Google Scholar

[44] Jha P, Chandra BP. Survey of the literature on mechano-luminescence from 1605 to 2013. Luminescence, 2014, 29: 977-993 CrossRef PubMed Google Scholar

[45] Hurt CR, Mcavoy N, Bjorklund S, et al. High intensity triboluminescence in europium tetrakis (dibenzoylmethide)-triethyl-ammonium. Nature, 1966, 212: 179-180 CrossRef ADS Google Scholar

[46] Liu M, Wu Q, Shi H, et al. Progress of research on organic/organometallic mechanoluminescent materials. Acta Chim Sin, 2018, 76: 246-258 CrossRef Google Scholar

[47] Bünzli JCG, Wong KL. Lanthanide mechanoluminescence. J Rare Earths, 2018, 36: 1-41 CrossRef Google Scholar

[48] Sweeting LM, Rheingold AL. Crystal disorder and triboluminescence: Triethylammonium tetrakis(dibenzoylmethanato)europate. J Am Chem Soc, 1987, 109: 2652-2658 CrossRef Google Scholar

[49] Rheingold AL, King W. Crystal structures of three brilliantly triboluminescent centrosymmetric lanthanide complexes: Piperidinium tetrakis(benzoylacetonato)europate, hexakis(antipyrine)terbium triiodide, and hexaaquadichloroterbium chloride. Inorg Chem, 1989, 28: 1715-1719 CrossRef Google Scholar

[50] Takada N, Hieda S, Sugiyama J, et al. Mechanoluminescence from piezoelectric crystals of an europium complex. Synth Met, 2000, 111-112: 587-590 CrossRef Google Scholar

[51] Hasegawa Y, Kitagawa Y, Nakanishi T. Effective photosensitized, electrosensitized, and mechanosensitized luminescence of lanthanide complexes. NPG Asia Mater, 2018, 10: 52-70 CrossRef ADS Google Scholar

[52] Brites CDS, Balabhadra S, Carlos LD. Lanthanide-based thermometers: At the cutting-edge of luminescence thermometry. Adv Opt Mater, 2019, 7: 1801239 CrossRef Google Scholar

[53] Wang X, Wolfbeis OS, Meier RJ. Luminescent probes and sensors for temperature. Chem Soc Rev, 2013, 42: 7834 CrossRef PubMed Google Scholar

[54] Williams CA, Blake AJ, Wilson C, et al. Novel metal-organic frameworks derived from Group II metal cations and aryldicarboxylate anionic ligands. Cryst Growth Des, 2008, 8: 911-922 CrossRef Google Scholar

[55] Pan C, Nan J, Dong X, et al. A highly thermally stable ferroelectric metal-organic framework and its thin film with substrate surface nature dependent morphology. J Am Chem Soc, 2011, 133: 12330-12333 CrossRef PubMed Google Scholar

[56] Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169-11186 CrossRef PubMed ADS Google Scholar

[57] Blöchl PE. Projector augmented-wave method. Phys Rev B, 1994, 50: 17953-17979 CrossRef PubMed ADS Google Scholar

[58] Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865-3868 CrossRef PubMed ADS Google Scholar

[59] Monkhorst HJ, Pack JD. Special points for brillouin-zone integrations. Phys Rev B, 1976, 13: 5188-5192 CrossRef ADS Google Scholar

[60] Wang V, Xu N, Liu JC, et al. VASPKIT: A pre- and post-processing program for VASP code. 2019, arXiv: 1908.08269. Google Scholar

[61] Guo Q, Wang Q, Jiang L, et al. A novel apatite, Lu5(SiO4)3N:(Ce,Tb), phosphor material: Synthesis, structure and applications for NUV-LEDs. Phys Chem Chem Phys, 2016, 18: 15545-15554 CrossRef PubMed ADS Google Scholar

[62] Dorenbos P. Systematic behaviour in trivalent lanthanide charge transfer energies. J Phys-Condens Matter, 2003, 15: 8417-8434 CrossRef ADS Google Scholar

[63] Dorenbos P. The Eu3+ charge transfer energy and the relation with the band gap of compounds. J Lumin, 2005, 111: 89-104 CrossRef ADS Google Scholar

[64] Lin SH, Wutz D, Ho ZZ, et al. Mechanisms of triboluminescence. Proc Natl Acad Sci USA, 1980, 77: 1245-1247 CrossRef PubMed ADS Google Scholar

[65] Chandra BP. Mechanoluminescence and piezoelectric behaviour of molecular crystals. Phys Stat Sol A, 1981, 64: 395-405 CrossRef ADS Google Scholar

[66] Eddingsaas NC, Suslick KS. Light from sonication of crystal slurries. Nature, 2006, 444: 163 CrossRef PubMed ADS Google Scholar

[67] Mukherjee S, Thilagar P. Renaissance of organic triboluminescent materials. Angew Chem Int Ed, 2019, 58: 7922-7932 CrossRef PubMed Google Scholar

[68] Guo X, Zhu G, Li Z, et al. A lanthanide metal-organic framework with high thermal stability and available Lewis-acid metal sites. Chem Commun, 2006, : 3172-3174 CrossRef PubMed Google Scholar

  • Figure 1

    Crystal structure (a) and SEM image (b) of SBD. (c) PXRD patterns of the as-synthesized SBD and Tb-SBD.

  • Figure 2

    (a) EDX mapping, (b) fluorescence micrograph and (c) rietveld refinement of Tb-SBD. The inserted table in (c) shows the comparison of cell parameters before and after Tb doping. (d) Distorted bi-capped coordination octahedron of the Sr2+ and Tb3+ ions in Tb-SBD.

  • Figure 3

    (a) Calculated band structure of SBD and the corresponding projected DOS on elements. (b) Diffuse reflectance spectra of SBD; the inset shows the corresponding Tauc plot. Excitation vs. emission wavelength contour plot for PL intensity in (c) SBD and (d) Tb-SBD, where PLE means PL excitation.

  • Figure 4

    (a) ML spectra of SBD and Tb-SBD upon grinding. (b) CL spectra of Tb-SBD under different accelerating voltages. (c) Schematic of ML mechanism in Tb-SBD.

  • Figure 5

    (a) Multicolor ML spectra and (b) Commission Internationale de l´Eclairage (CIE) chromaticity coordinates of Ln-SBD (Ln = Tb, Dy, Sm, Eu). (c) Multicolor ML spectra, (d) CIE chromaticity coordinates and (e) ML images of Tb1−xEux-SBD (x = 0.2, 0.4, 0.6, 0.8).

  • Figure 6

    (a) ML spectra of Tb0.8Eu0.2-SBD at different temperatures which are normalized at 544 nm. (b) ML intensity ratio (I618/I544) of Tb0.8Eu0.2-SBD as a function of temperature (red dots); white line is the fitting curve and all error bars are based on means ± standard deviation (n = 3).(c) Relative sensitivity of temperature sensing based on the ML intensity ratio of Eu/Tb in Tb0.8Eu0.2-SBD.


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