Mixed-Lanthanide MetalâOrganic Frameworks with Tunable Color and

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Mixed-lanthanide metal-organic frameworks with tunable color and white light emitting Yanli Gai, Qin Guo, Kecai Xiong, Feilong Jiang, Chenyuan Li, Xin Li, Yan Chen, Chengyuan Zhu, Qing Huang, Rui Yao, and Maochun Hong Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.6b01541 • Publication Date (Web): 24 Jan 2017 Downloaded from http://pubs.acs.org on January 25, 2017

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Crystal Growth & Design

Mixed-lanthanide metal-organic frameworks with tunable color and white light emitting 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 ABSTRACT: Three isostructural lanthanide metal-organic frameworks (Ln-MOFs, Ln = Eu3+, Tb3+, Dy3+) containing P-terphenyl-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 emitting. Additionally, tunable luminescence can be also achieved by changing the excitation wavelength. Lanthanide remains attractive due to their highly monochromatic emissions arising from 4fn→4fn transitions1-4, which make them popular materials with application in display device 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

ACS Paragon Plus Environment


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compared to the traditional way. Lanthanide metal-organic frameworks (Ln-MOFs) are definitely the promising backbones, since different lanthanide chromophores can be controllable incorporated, leading to generate emitters in the whole visible region. Especially, europium and terbium MOFs play an important role to produce 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 chromophores’s proportion and the energy transfer process between them,23-25 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 has 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 this 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 depended energy transfer between lanthanide emissive levels and the excitation wavelength of mixed Ln-MOFs, it enables effective color tuning in the visible region, including white light emitting.


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Fig. 1 Coordination environment around Eu3+ ion in Eu(HL)(H2O)(DEF) (30% ellipsoids) with hydrogen atoms being omitted for clarity. 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 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.36-37 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 Ln-MOFs 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 (Fig. S1). Here, Eu-MOF, Eu(HL)(H2O)(DEF), is chosen as a representative to discuss the structure. It crystallizes in P-1 space group with a triclinic system, and exhibits three dimensional structure based on [Ln2(µ2-COO)4(COO)4]2metallic dimers. As shown in Fig. 1, the coordination geometry around Eu3+ features in a distorted anti-prism 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



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dimers, which are further linked by HL3- to generate a three dimensional framework (Fig. 2).

Fig. 2 The 3D framework of Eu(HL)(H2O)(DEF) viewing at the (1 0 0) plane. The triplet state energy of H4L (20800 cm-1) estimated by the 77 K phosphorescence spectrum (Fig. S2) of the Gd-MOF38-40 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 Ln-MOFs has been investigated. As shown in Fig. 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

Fig.

S3.

The

mixed

Ln-MOFs,

(EuxTbyDy1-x-y)(HL)(H2O)(DEF), show 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 5

D0→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.


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Fig. 3 The emission spectra of Eu-, Tb-, and Dy-MOFs excited at 336 nm in the solid state, respectively, normalized by Eu3+ emission at 612 nm. Insert: CIE chromaticity diagram for each Ln-MOFs. 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 Fig. 4a, the green component of the emission from Tb3+ (5D4→7F5) increases steadily upon lowing the temperature, whereas the red component from Eu3+ (5D0→7F2) displays the opposite behavior. Such observation should attribute 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 K to 50 K as depicted in Fig. 4b. Interestingly, the white light emissions happen when the temperature turn to be 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 deep pink to green-yellow and/or from yellow to green-yellow during 300 K and 50 K (Fig. S4 and S5) as the excitation wavelength is changed to 363 nm and/or 387 nm.



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Fig.4 Solid state emission spectra of (Eu0.0667Tb0.0667Dy0.8666)(HL)(H2O)(DEF) excited at 336 nm under temperature from 300 K 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 K to 50 K (b). Similar temperature and excitation wavelength depended color modulation of (Eu0.0666Tb0.4667Dy0.4667)(HL)(H2O)(DEF) is also reported (Fig. 5a and 5b). As depicted in Fig. 5b, emission colors vary between light pink, white and green-yellow (excited at 363 nm) when the temperature varies between 300 K and 50 K. Interestingly, when the temperature is 200 K and/or 150 K, the emission colors turn to be 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 (Fig. 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 al43,46-48, Zhang et al45 and Carlos et al44,49, except for the emission color. Generally, the emission color in most of the reported work mentioned above 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 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


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also the rarely reported example of mixed Ln-MOF with white light modulated by temperature.

Fig.5 Solid state emission spectra of (Eu0.0666Tb0.4667Dy0.4667)(HL)(H2O)(DEF) excited at 363 nm under different temperature from 300 K 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 K to 50 K (b). In summary, a series of Ln-MOFs and mixed Ln-MOFs have been synthesized by 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. ASSICIATED CONTENT Supporting Information Synthesized method, structure information, PXRD, ICP, TGA, and other additional spectra. CCDC 1496815-1496817 contains the supplementary crystallographic data for Eu-, Tb- and Dy-MOFs. This material is available as electronic supplementary information via the internet at http://pubs.acs.org.



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AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected] (Kecai Xiong); [email protected] (Maochun Hong). ACKNOWLEDGEMENT We are thankful for financial support from the National Natural Science Foundation of China (No. 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. REFERENCES (1) Bunzli, J. C. G.; Eliseeva, S. V. Intriguing Aspects of Lanthanide Luminescence. Chem. Sci. 2013, 4, 1939-1949. (2) Carlos, L. D.; Ferreira, R. A. S.; Bermudez, V. D.; Julian-Lopez, B.; Escribano, P. Progress on Lanthanide-based Organic-inorganic Hybrid Phosphors. Chem. Soc. Rev. 2011, 40, 536-549. (3) Moore, E. G.; Samuel, A. P. S.; Raymond, K. N. From Antenna to Assay: Lessons Learned in Lanthanide Luminescence. Acc. Chem. Res. 2009, 42, 542-552. (4) Eliseeva, S. V. Luminescence of Lanthanide Ions in Coordination Compounds and Nanomaterials. Angew. Chem. Int. Ed. 2015, 54, 8598-8598. (5) Andres, J.; Hersch, R. D.; Moser, J. E.; Chauvin, A. S. A New Anti-Counterfeiting Feature Relying on Invisible Luminescent Full Color Images Printed with Lanthanide-Based Inks. Adv. Funct. Mater. 2014, 24, 5029-5036. (6) Liu, J.; Miao, J. S.; Wu, H. B. Efficient Solution-processed Double-layer Red OLEDs Based on a New Europium Complex With a Carbazole Group. Luminescence 2015, 30, 393-396. (7) Won, Y. H.; Jang, H. S.; Im, W. B.; Jeon, D. Y.; Lee, J. S. Tunable full-color-emitting La0.827Al11.9O19.09:Eu2+, Mn2+ Phosphor for Application to Warm


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(40) [Gd(HL)(H2O)(DEF)]n is obtained according to the method that reported in this paper, and its structure information is listed in supporting information, (41) Crosby, G. A.; Alire, R. M.; Whan, R. E. Intramolecular Energy Transfer in Rare Earth Chelates - Role of Triplet State. J. Chem. Phys. 1961, 34, 743. (42) Weissman, S. I. Intramolecular Energy Transfer - The Fluorescence of Complexes of Europium. J. Chem. Phys. 1942, 10, 214-217. (43) Rao, X. T.; Song, T.; Gao, J. K.; Cui, Y. J.; Yang, Y.; Wu, C. D.; Chen, B. L.; Qian, G. D. A Highly Sensitive Mixed Lanthanide Metal-Organic Framework Self-Calibrated Luminescent Thermometer. J. Am. Chem. Soc. 2013, 135, 15559-15564. (44) Ananias, D.; Paz, F. A. A.; Yufit, D. S.; Carlos, L. D.; Rocha, J. Photoluminescent Thermometer Based on a Phase-Transition Lanthanide Silicate with Unusual Structural Disorder. J. Am. Chem. Soc. 2015, 137, 3051-3058. (45) Meng, X.; Song, S. Y.; Song, X. Z.; Zhu, M.; Zhao, S. N.; Wu, L. L.; Zhang, H. J. A Eu/Tb-codoped Coordination Polymer Luminescent Thermometer. Inorg. Chem. Front. 2014, 1, 757-760. (46) Lian, X. S.; Zhao, D.; Cui, Y. J.; Yang, Y.; Qian, G. D. A Near Infrared Luminescent

Metal-organic

Framework

for

Temperature

Sensing

in

The

Physiological Range. Chem. Commun. 2015, 51, 17676-17679. (47) Cui, Y. J.; Zhu, F. L.; Chen, B. L.; Qian, G. D. Metal-organic Frameworks for Luminescence Thermometry. Chem. Commun. 2015, 51, 7420-7431. (48) Cui, Y. J.; Xu, H.; Yue, Y. F.; Guo, Z. Y.; Yu, J. C.; Chen, Z. X.; Gao, J. K.; Yang, Y.; Qian, G. D.; Chen, B. L. A Luminescent Mixed-lanthanide Metal-organic Framework Thermometer. J. Am. Chem. Soc. 2012, 134, 3979-3982. (49) Brites, C. D.; Lima, P. P.; Silva, N. J.; Millan, A.; Amaral, V. S.; Palacio, F.; Carlos, L. D. A Luminescent Molecular Thermometer for Long-term Absolute Temperature Measurements at The Nanoscale. Adv. Mater. 2010, 22, 4499-4504. (50) Yang, Q. Y.; Pan, M.; Wei, S. C.; Li, K.; Du, B. B.; Su, C. Y. Linear Dependence of Photoluminescence in Mixed Ln-MOFs for Color Tunability and Barcode Application. Inorg. Chem. 2015, 54, 5707-5716.



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For Table of Contents Use Only

Mixed-lanthanide metal-organic frameworks with tunable color and white light emitting Yanli Gai†, Qin Guo†, Kecai Xiong†*, Feilong Jiang‡, Chenyuan Li†, Xin Li†, Yan Chen†, Chengyuan Zhu†, Qing Huang†, Rui Yao†, and Maochun Hong‡*

The

color-tunable

luminescence

behavior

of

mixed

Ln-MOFs,

(EuxTbyDy1-x-y)(HL)(H2O)(DEF), is found by rationally modulating the temperature and excitation wavelength. Importantly, by tuning the temperature, the emission colors change broadly in the visible region and lead to the production of white light with the CIE coordinate being (0.30, 0.32), which is necessary for the fabrication of full-color display devices.


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