Mixed-Lanthanide Metal–Organic Frameworks with Tunable Color and

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Mixed-Lanthanide Metal−Organic Frameworks with Tunable Color and White Light Emission Yanli Gai,† Qin Guo,† Kecai Xiong,*,† Feilong Jiang,‡ Chenyuan Li,† Xin Li,† Yan Chen,† Chengyuan Zhu,† Qing Huang,† Rui Yao,† and Maochun Hong*,‡ †

School of Chemistry and Chemical Engineering & Jiangsu Key Laboratory of Green Synthetic Chemistry for Functional Materials, Jiangsu Normal University, Xuzhou, Jiangsu 221116, P.R. China ‡ Key Lab of Coal to Ethylene Glycol and Its Related Technology, State Key Lab of Structure Chemistry, Fujian Institute of Research on the Structure of Matter, University of Chinese Academy of Sciences, Fuzhou, Fujian 350002, P.R. China S Supporting Information *

ABSTRACT: Three isostructural lanthanide metal−organic frameworks (Ln-MOFs, Ln = Eu3+, Tb3+, Dy3+) containing Pterphenyl-2,2″,4,4″-tetracarboxylate ligand (H4L) with red, green, and blue luminescence were solvothermally synthesized. Thus, a series of mixed Ln-MOFs, (EuxTbyDy1‑x‑y)(HL)(H2O)(DEF) (DEF, N,N-diethylformamide), were designed and obtained, which displayed highly temperature-tuned emission in the visible region, including white light emission. Additionally, tunable luminescence can also be achieved by changing the excitation wavelength.

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which is the real challenge. Meanwhile, research on white light emitting material in a single backbone is still on the way, despite some of the work having been reported.26−29 Carboxylate acids are usually chosen as photosensitizers to construct the lanthanide MOFs, not only because they are more likely to coordinate with lanthanide, but also because these kind of ligands are capable of absorbing and transferring energy to lanthanide effectively,30−35 in which way the introduction of carboxylate acids acting as the light antenna is able to overcome the weak absorption of lanthanide. Herein, we report some isostructural Eu-, Tb-, and Dy-MOFs with the formulation of Ln(HL)(H2O)(DEF) (DEF, N,N-diethylformamide), based on P-terphenyl-2,2″,4,4″-tetracarboxylic acid (H4L), and their corresponding mixed Ln-MOFs, (EuxTbyDy1‑x‑y)(HL)(H2O)(DEF), which were synthesized via controlling the ratios of lanthanide sulfates used in the reaction. Furthermore, by modulating the temperature dependent energy transfer between lanthanide emissive levels and the excitation

anthanide remains attractive due to their highly monochromatic emissions arising from 4fn → 4fn transitions,1−4 which make them popular materials with application in display devices that focus on full-color display mainly consisting of white and tunable pure color emitters. Traditionally, most color-tunable materials are mixtures generated typically by mixing different color emitting materials together.5−8 An alternative approach is making couples of chromophores emit simultaneously in a single-component backbone,9−13 which has a significant improvement in stability, reproduction, and fabrication process compared to the traditional way. Lanthanide metal−organic frameworks (Ln-MOFs) are definitely the promising backbones, since different lanthanide chromophores can be controllably incorporated, leading to generate emitters in the whole visible region. Especially, europium and terbium MOFs play an important role in producing the primary red and green elements.14−17 Generally, multiple emissions can be achieved by adjusting the proportion of different color via controlling the lanthanide ratio and the excitation wavelength in the mixed Ln-MOFs.18−22 However, the design and synthesis of such color-tunable materials in a single-component backbone actually require precise modulation of each chromophore’s proportion and the energy transfer process between them,23−25 © 2017 American Chemical Society

Received: October 20, 2016 Revised: January 24, 2017 Published: January 24, 2017 940

DOI: 10.1021/acs.cgd.6b01541 Cryst. Growth Des. 2017, 17, 940−944

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wavelength of mixed Ln-MOFs, it enables effective color tuning in the visible region, including white light emission. Reaction of Ln2(SO4)3·8H2O and H4L in H2O/DEF has afforded three novel Ln-MOFs with the formulation being Ln(HL)(H2O)(DEF) (Ln = Eu3+, Tb3+, and Dy3+). Generally, because of the similar coordination behavior of different lanthanide ions, various Ln3+ ions can be introduced into one Ln-MOF simultaneously with Ln3+ ions distributing randomly over the metal sites. 3 6 , 3 7 Thus, mixed Ln-MOFs, (EuxTbyDy1‑x‑y)(HL)(H2O)(DEF), were synthesized according to the method mentioned above by using mixed lanthanide sulfates instead. Relative Ln3+ ratios in the resulting mixed LnMOFs are further confirmed by inductively coupled plasma spectroscopy (ICP). The structures of all Ln-MOFs and mixed Ln-MOFs are isostructural to each other confirmed by the single-crystal X-ray diffraction as well as the powder X-ray diffraction (Figure S1). Here, Eu-MOF, Eu(HL)(H2O)(DEF), is chosen as a representative to discuss the structure. It crystallizes in P1̅ space group with a triclinic system, and exhibits three-dimensional structure based on [Ln2(μ2COO)4(COO)4]2− metallic dimers. As shown in Figure 1,

Figure 2. 3D framework of Eu(HL)(H2O)(DEF) viewing at the (1 0 0) plane.

Figure 3. Emission spectra of Eu-, Tb-, and Dy-MOFs excited at 336 nm in the solid state, respectively, normalized by Eu3+ emission at 612 nm. Inset: CIE chromaticity diagram for each Ln-MOFs.

Figure 1. Coordination environment around Eu3+ ion in Eu(HL)(H2O)(DEF) (30% ellipsoids) with hydrogen atoms being omitted for clarity.

emission peaks mainly from the emissive states of Eu3+ and Tb3+ ions, and the relatively weak emission band during 380− 450 nm comes from the coordinated ligand. The most intense peak at 612 nm arising from 5D0 → 7F2 of Eu3+ ion is dominant in the whole spectra at room temperature. The emission intensity changes as the Eu3+, Tb3+, and Dy3+ concentration changed. By optimizing the ratios of Eu3+, Tb3+, and Dy3+ ions, (Eu0.0667Tb0.0667Dy0.8666)(HL)(H2O)(DEF) is obtained and chosen to illustrate the color-tunable luminescent behavior. As shown in Figure 4a, the green component of the emission from Tb3+ (5D4 → 7F5) increases steadily upon lowering the temperature, whereas the red component from Eu3+ (5D0 → 7 F2) displays the opposite behavior. Such an observation should be attributed to the temperature dependent Tb3+-to-Eu3+ intermetallic energy transfer, and this kind of energy transfer becomes less efficient when the temperature decreases.43−45 Therefore, emission colors vary between orange and white excited at 336 nm as the temperature varies from 300 to 50 K as depicted in Figure 4b. Interestingly, the white light emission happens when the temperature becomes 100 and 50 K, with the CIE coordinates being (0.32, 0.25) at 100 K and (0.30, 0.32) at 50 K that are very close to those of the pure white light (0.33, 0.33). However, the emission color changes gradually from

the coordination geometry around Eu3+ features in a distorted antiprism consisting of four μ2-bridging and two monodentate carboxylate oxygen atoms from HL3− together with two oxygen atoms each from DEF and water molecule. Eu3+ ion and its symmetry-formed Eu3+ ion are connected via four bridging carboxylate acids to form metallic dimers, which are further linked by HL3− to generate a three-dimensional framework (Figure 2). The triplet state energy of H4L (20 800 cm−1) estimated by the 77 K phosphorescence spectrum (Figure S2) of the GdMOF38−40 matches well with the emissive level of Eu3+ ion, indicating that H4L can sensitize Eu3+ luminescence more effectively.41,42 Solid-state luminescence behavior of each LnMOF has been investigated. As shown in Figure 3, Eu-MOF displays red emission centered at 579, 593, 612, 650, and 700 nm that can be assigned to 5D0 → 7FJ (J = 0−4), and Tb-MOF displays green emission at 488, 545, 583, and 620 nm from 5D4 → 7FJ (J = 6−3) with the excitation wavelength at 336 nm (ligand absorption), while Dy-MOF displays blue emission excited at 336 nm mainly from the coordinated ligand. Corresponding excitation spectra are listed in Figure S3. The mixed Ln-MOFs, (EuxTbyDy1‑x‑y)(HL)(H2O)(DEF), show 941

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Figure 4. Solid-state emission spectra of (Eu0.0667Tb0.0667Dy0.8666)(HL)(H2O)(DEF) excited at 336 nm under temperature from 300 to 50 K (a); CIE chromaticity diagram of (Eu0.0667Tb0.0667Dy0.8666)(HL)(H2O)(DEF) excited at 336 nm as the temperature changes from 300 to 50 K (b).

Figure 5. Solid-state emission spectra of (Eu0.0666Tb0.4667Dy0.4667)(HL)(H2O)(DEF) excited at 363 nm under different temperatures from 300 to 50 K (a). CIE chromaticity diagram of (Eu0.0666Tb0.4667Dy0.4667)(HL)(H2O)(DEF) excited at 363 nm as the temperature changes from 300 to 50 K (b).

light-emitting mixed Ln-MOFs were obtained by tuning the lanthanide composition and excitation wavelength.9,19,21,22,50 Interestingly, this work displays temperature modulating emission between orange and white, and/or pink, white, and green−yellow, which is also the rarely reported example of mixed Ln-MOF with white light modulated by temperature. In summary, a series of Ln-MOFs and mixed Ln-MOFs have been synthesized by the hydrothermal method. Their structures and optical properties were studied. The mixed Ln-MOFs, (EuxTbyDy1‑x‑y)(HL)(H2O)(DEF), easily allow incorporation of three primary colors into one framework. The color-tunable luminescence behavior of these mixed Ln-MOFs is found by rationally modulating the temperature and excitation wavelength. Importantly, by tuning the temperature, the emission colors change broadly and lead to the production of white light, which is necessary for the fabrication of full-color display devices.

deep pink to green−yellow and/or from yellow to green− yellow during 300 and 50 K (Figures S4 and S5) as the excitation wavelength is changed to 363 nm and/or 387 nm. Similar temperature and excitation wavelength depended color modulation of (Eu0.0666Tb0.4667Dy0.4667)(HL)(H2O)(DEF) is also reported (Figure 5a,b). As depicted in Figure 5b, emission colors vary between light pink, white, and green− yellow (excited at 363 nm) when the temperature varies between 300 and 50 K. Interestingly, when the temperature is 200 K and/or 150 K, the emission colors become white with the CIE coordinates being (0.31, 0.25) and/or (0.30, 0.30). However, its emission color varies during the region of orange, yellow, and green−yellow (Figures S6, S7) as the excitation wavelength changed to 336 nm and/or 387 nm. Such behavior of temperature tuning emission caused by the variation of energy transfer efficiency between lanthanide ions is similar to the previously reported work by Qian and Chen et al.,43,46−48 Zhang et al.,45 and Carlos et al.,44,49 except for the emission color. Generally, the emission color in most of the reported work mentioned here changes between the regions of red, orange, green−yellow, and green rather than white when the temperature decreases. In addition, most of the reported white-

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.6b01541. 942

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Synthesized method, structure information, PXRD, ICP, TGA, and other additional spectra (PDF) Accession Codes

CCDC 1496815−1496817 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. *E-mail: [email protected]. ORCID

Kecai Xiong: 0000-0003-0384-8560 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We are thankful for financial support from the National Natural Science Foundation of China (Nos. 21501075, 21501076, and 21390392), the Natural Science Foundation of Jiangsu Province of China (No. BK20150226), Undergraduate Students Project of Jiangsu Province, TAPP of Jiangsu Higher Education Institutions, and PAPD of Jiangsu Higher Education Institutions.

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