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Article
Metal-Organic Frameworks Modulated by
Doping Er for Up-conversion Luminescence
3+

Xindan Zhang, Bin Li, Heping Ma, Liming Zhang, and Haifeng Zhao
ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.6b03841 • Publication Date (Web): 17 Jun 2016
Downloaded from http://pubs.acs.org on June 26, 2016

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1
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7 Metal-Organic Frameworks Modulated by Doping Er3+ for Up-
8
9 conversion Luminescence
10
11 Xindan Zhang,a,b Bin Li,*a Heping Ma,*a Liming Zhang,a and Haifeng Zhaoa
12 [a]
13 State Key Laboratory of Luminescence and Applications, Changchun Institute of Optics Fine Mechanics and
14 Physics, Chinese Academy of Sciences, Changchun 130033, P. R. China
[b]
15 University of Chinese Academy of Sciences, Beijing 100049, PR China
16
17 KEYWORDS: up-conversion materials, metal-organic frameworks, near infrared excitation, rare earth metal and
18 excited state absorption (ESA)
19
20
21 ABSTRACT: Here we present metal-organic frameworks prepared by one-step synthesis method, possessing both archi-
22 tectural properties of MOF building and up-conversion luminescence of rare earth Er3+ (hereafter denoted as Up-MOFs).
23 Up-MOFs have characteristic up-conversion emissions at 520nm, 540nm and 651nm under the excitation of 980nm owing
24 to the multiple photons absorption. The up-conversion mechanism of these Up-MOFs has been discussed, and it can be
25 attributed to excited state absorption process. The design and synthesis of Up-MOF materials possessing near-infrared
26 region excitation and up-conversion luminescence are fully expected to be candidates for the advancement of applica-
27 tions in bioimaging, sensors, optoelectronics, and energy conversion/storage devices.
28
29
30
INTRODUCTION Modern medical assay technologies mentioned above,
31
32 where near infrared excitation plays a vital part are usual-
In the past decade, up-conversion materials which have
33 ly based on photoluminescence method.10-12 The tradi-
excitation at near-infrared region (NIR) and emission at
34 tional carriers for sensors or drug, such as SiO2 and
visible region via a sequential absorption process of mul-
35 MOFs, always need to offer extra space for luminescent
tiple photons have drawn wide attention among a grow-
36 materials which commonly provide the optical signal and
ing body of researchers.1-3 Benefit from both the promis-
37 then act as the markers after being excited, resulting in
ing feature of being excited by NIR which is generally
38 relatively poor luminescence efficiency and bulky size of
deemed as the “optical window in biological tissue” due to
39 assay system. In responding to improve such medical ap-
its reinforced light penetration depth and minimized au-
40 plications, a novel porous material with intrinsic lumines-
to-fluorescent interference,4 and intrinsic luminescent
41 cence arouses our great interest.
advantages such as sharp emission lines, long lifetimes
42 and superior photostability,5 up-conversion materials are
43 Metal organic frameworks (MOFs) are emerging porous
extremely suitable for the applications in biological imag- materials with hybrid inorganic-organic structure which
44 ing, photovoltaics and photodynamical therapeutics.6-9
45 comes from an assembly of metal clusters and organic
Thus there has been extensive investigations aiming at building blocks.13-15 Benefit from the well-organized poros-
46 fabrication and exploitation of up-conversion materials.
47 ity and versatile chemical functionality, MOFs are of tre-
Among these researches, most up-conversion material mendous attractiveness and great value in many fields
48 synthesis are usually focused on nanocrystals which are
49 such as gas storage and separation16-18, catalysis19, smart
composed of oxides ( Y2O3, ZnO, Yb3Al5O12, and so on) or sensors20-23, and drug delivery24, 25. As a unique type of
50 fluorides (CaF2, NaYF4, KMnF3, and so on) acting as inor-
51 MOFs, the lanthanide MOFs (Ln-MOFs) have drawn ex-
ganic host matrix, and embedded lanthanide ions (such tensive attention due to their excellent luminescent char-
52 as Er3+, Tm3+, Ho3+) acting as luminescence centers. There-
53 acter coming from doped lanthanide. Their intrinsic fea-
fore, exploiting new up-conversion systems such as inor- tures of lanthanides together with the advantages of MOF
54 ganic-organic composite systems may achieve property
55 structure provide eminent expectation for developing
synergies of inorganic rare earth ion and organic func- novel luminescent materials. By rational choices of rare
56 tional group targeting multi-applications.
57 earth ion and organic ligands, synthesis process of Ln-
58 MOFs has much flexibility of being elaborately controlled
and tailored for featured luminescence properties.26 Re-
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cently, several luminescent MOFs have been put forward er diluent RE3+ could be adjusted by need on the premise
1 by introducing various luminescent rare earth ions into of total RE3+ was 0.1 mmol. And white crystalline powder
2 basic frameworks, and these MOFs have been widely used was obtained following the identical means of preparation
3 as fluorescence chemical sensors. However the excitation of standard Up-MOF mentioned previously.
4 wavelengths of these MOFs are mostly located at the ul-
5 traviolet region, in which situation the disadvantages of RESULTS AND DISCUSSION
6 weak penetrability and auto-fluorescence interference
7 from tissues and organs still exist and limit their applica- Morphology and Structure of Up-MOFs.
8 tions in biology to a large extent. Undoubtedly, the fabri-
9 cation of MOF materials possessing up-conversion lumi- Different from the conventional post-synthetic modifica-
10 nescence which have excitation at near infrared region is tion (PSM)29 of MOFs in which situation chemical modifi-
11 becoming a promising candidate for the advancement of cations are performed after the preparation of MOFs, Up-
12 applications in bioimaging, sensors, optoelectronics, drug MOFs of RE(BTC)(H2O)•DMF, where RE could be Er3+,
13 tracing and energy conversion/storage devices. Y3+, Lu3+, Gd3+ or Yb3+ and BTC= 1,3,5-Benzenetricarboxylic
14 acid, were one-step synthesized through a solvothermal
15 Given the favorable structure of MOFs which could be method similar with the study reported previously.30 So-
16 modulated to finely optimize the photoluminescence per- dium acetate is selected as capping reagent in order to
17 formance of lanthanide ions, there is an ever-increasing modulate crystal morphology and size. The resultant Up-
18 interest in design and synthesis of porous MOF material MOF is a 3D porous framework crystallized in P4322 space
19 with intrinsic up-conversion luminescence.27, 28 Here we group. Every building unit includes one rare earth ion
20 report the study on one-step strategy to prepare Er-doped (such as Er3+, Y3+) with seven coordination sites, bonding
21 Ln-MOFs with up-conversion luminescence (hereafter with one BTC ligand and one coordinated water molecule.
22 denoted as Up-MOFs) with uniform shape and tunable As depicted in Scheme 1(a), the special connection mode
23 size. The Up-MOFs doped with Er3+ have characteristic of rare earth ions results in a one-dimensional helical
24 up-conversion emissions at 520nm, 540nm and 651nm chain along the [001] direction. And then, inorganic
25 under the excitation at 980nm owing to the multiple pho- chains in one dimension connected by phenyl groups
26 tons absorption process. Furthermore, the up-conversion along [100] and [010] directions give rise to a framework
27 mechanism of these Up-MOFs has been deeply discussed in three dimension (as depicted in Scheme 1(b)).31
28 and attributed to excited state absorption (ESA). The fine-
29 organized porosity and attractive luminescent properties
30 of Up-MOF make it feasible for us to exploit the carrier
31 suitable for detectable drug release or chemical sensing
32 under near-infrared excitation. Furthermore, we also
33 speculate the potential utility of such Up-MOF in energy
34 & environment applications by virtue of its superior phys-
35 ical, chemical, and optical properties.
36
37 EXPERIMENTAL SECTION
38
39 Procedure for Synthesis of Standard Up-MOF. Scheme 1. (a) 1D chains views in Up-MOFs along [001]
40 direction; (b) 3D structure images of (001) faces in Up-
41 A homogeneous mixture of ErCl3·6H2O (0.006 mmol),
MOFs with 1D channels. (C atom: gray; O atom: red; rare
42 YCl3·6H2O (0.094 mmol), H3BTC (0.1 mmol), NaAc•3H2O
earth ions: bright blue; H atoms are omitted for clarity)
43 (0.1 mmol), N,N-dimethylformamide (8 mL) and deion-
44 ized water (4 mL) was added into a sealed vial. Then the The structures of the as-synthesized samples are demon-
45 reaction vessel was heated at 60 °C for one day. The sam- strated by powder XRD pattern and presented in Figure 1.
46 ples were washed with N,N-dimethylformamide for sever- The PXRD patterns which are well conformed to previous
47 al times. Above products were activated by being soaked literatures, suggest that Up-MOFs are isostructural and
48 in methanol lasting one day (each time using 50 mL of well-indexed to the known bulk phase of JUC-32.32 As de-
49 methanol and fresh methanol every six hours). The final picted in Figure 1, PXRD patterns of Up-MOF-Y/Er (black
50 products were separated by filtering and dried under vac- line, d) and other Up-MOFs doped with different rare
51 uum at 80 °C for 12 h. earth ions at same concentration ratio of rare earth to
52 H3BTC are almost identical, indicating the unchanged
Procedure for Synthesis of Other Types of Up-MOF.
53 crystal structure after ion replacement because of the
54 same coordination numbers and modes of diverse rare
Y3+ could be replaced by other rare earth ions such as earth ions of Er3+, Y3+, Gd3+, Lu3+, or Yb3+. The slight shift
55
Yb3+, Gd3+, or Lu3+. Given the same coordination numbers
56
and modes, the concentration ratio between Er3+ and oth-
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of diffraction peaks of Up-MOFs in our case can be ex-

1 plained by the lanthanide contraction.15
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13
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15 Figure 2. SEM images of standard Up-MOF crystals syn-
16 thesized with (a)(b)and without (c)(d) addition of sodium
17 acetate at different magnifications. Scale bars: 1μm (a, c),
18 500 nm (b, d).
19
20 Figure 1. PXRD patterns of Up-MOFs (a) the simulated, The permanent porosity of Up-MOFs-Y/Er is demonstrat-
21 (b) doped with Gd/Er, (c) doped with Lu/Er, (d) doped ed by measuring N2 adsorption at 77K. Before the meas-
22 with Y/Er, (e) doped with Yb/Er and (f) totally doped with urement, the samples were treated with degasing at 200
23 Er. °C overnight. As depicted in Figure S2, Up-MOFs display
24 a typical characteristic of microporous materials which
25 The morphologies of the standard Up-MOF are moni- has widely used as drug carrier.31, 34 The calculated BET
26 tored by scanning electron microscopy. The SEM images surface area is 59.28 m2/g, and Langmuir surface area is
27 (Figure 2) exhibit that rod-like standard Up-MOFs are 72.87 m2/g. In order to investigate the feasibility of Up-
28 highly uniform crystals with the width of 0.4 μm and the MOF in drug release, we design primary measurement of
29 length of 2 μm. Here, sodium acetate acting as a capping drug release by using ibuprofen (IBU), which has been
30 reagent in process of MOFs formation besides BTC, pro- widely utilized as a model drug in research of drug deliv-
31 vides positive effects on the crystal quality and size. The ery and tracing. We monitor the absorption spectra of
32 influence of sodium acetate on controlling the MOF size supernatant after the IBU-loaded Up-MOFs were placed
33 and then generating relatively uniform morphology into PBS solution which is widely used for diluting biolog-
34 comes from its improvements in coordinating interac- icals. The absorption spectra and corresponding profiles
35 tions between the rare earth ions and organic ligands. In versus release time are shown in Figure S3, exhibiting the
36 the preliminary stage of crystal formation, RE3+ bond with capability of Up-MOFs in sustained drug release. These
37 the carboxylic groups from both organic linker of BTC results demonstrate that such Up-MOF system which
38 and sodium acetate added. Therefore the crystal growth is benefits from up-conversion characteristic and MOF
39 hindered in this period, resulting in more nuclei process. structure is promising as a candidate of the carrier used
40 Moreover, the competitive bonding between capping rea- for detectable drug release. Next, we desire to fully exam-
41 gents and BTC is speculated to regulate the rate of MOF ine the biocompatibility of such Up-MOFs for the further
42 formation.33 When no sodium acetate was added, we ob- biological applications.
43 serve the rod-like crystals with nonuniform phase from
44 SEM images (Figure 2c and 2d). Furthermore, the ele- Photoluminescence Properties of Up-MOFs.
45 mental analysis characterization of Up-MOF-Y/Er is in-
46 vestigated by EDX. As shown in Figure S1, representative In our case, Y3+ ion which lacks of 4f orbitals is relatively
47 peaks associated to Y, Er, C and O elements which consist inert to be a luminescent centre, therefore it just acts as
48 of standard Up-MOF together are clearly identified. the ion diluent and has negligible interaction with emit-
49 ting dopant of Er3+. The up-conversion luminescence
50 (UCL) spectra of the Up-MOF-Y1-χ/Erχ (χ is the mole frac-
51 tion of Er3+ in total RE3+) are tested under the 980 nm
52 excitation. As shown in Figure 3, Up-MOF-Y/Er with dif-
53 ferent Er3+concentration all exhibit characteristic emis-
54 sions at 520nm, 540 nm, and 651nm, respectively ascribed
55 to the allowed electronic transition from 2H11/2 to 4I15/2,
56 from 4S3/2 to 4I15/2 and from 4F9/2 to 4I15/2.35 Along with
57 increasing concentrations of Er3+ ions from 2% to 100% in
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mole fraction, the UCL intensity especially at 540nm ele-

1 vates at low Er3+concentration and reaches maxima at 6%
2 Er3+ content, corresponding to the maximum of quantum
3 yield of 0.1312%. Due to the concentration quenching ef-
4 fect, the UCL intensity of Up-MOF-Y/Er drastically de-
5 crease when the Er3+concentration is more than 10%. The
6 optimal concentration of doped Er3+ ions is demonstrated
7 to be 6%, beyond which the concentration quenching
8 effect will dominate over the increase of activator centers.
9 The concentration quenching originates from the larger
10 probability of energy loss at a killer center due to excita-
11 tion energy migration among activators of Er3+ at higher
12 concentration.36
13
14 Photoluminescence Mechanism of Up-MOFs.
15
16 Based on the understanding of traditional up-conversion Figure 4. UCL of Up-MOFs co-doped with Y, Yb, and Er
17 materials with inorganic matrix such as NaYF4:Yb3+/Er3+, in different molar ratio.
18 ion of Yb has always been selected as a sensitizer by
providing 2F5/2 energy level in energy transfer up- To further investigate the UC mechanism of Up-MOFs-
19
conversion (ETU) process.37 We fabricated the Up-MOFs Y0.94/Er0.06 (standard, mole ratio of Y:Er is 94:6), the rela-
20
co-doped with Y3+, Yb3+ and Er3+ (mole ratios of Y/Yb/Er tionship between pumping power and luminescent inten-
21
are 60/30/10, 30/60/10 and 0/90/10 respectively) to inves- sity has been measured (shown in Figure 5). Typically, for
22
tigate the effect of Yb3+, where Y3+ just act as a kind of ions an unsaturated up-conversion process, the emission in-
23
diluent because of a lack of 4f energy level. However, the tensity is strongly dependent on its local environment
24
spectra of Up-MOF-Y/Yb/Er with the distinctly different and obeys an empirical relation that is given as39, 40
25
26 doping concentration of Yb3+ show the same emission

 ∝  Equation (1)
27 intensity (Figure 4), indicating that the up-conversion
28 mechanism of Up-MOFs is speculated to arise from excit-
The relation demonstrates that the fluorescent intensity
29 ed state absorption of Er3+ by the interaction between
(
 ) is proportional to n th power of the excitation (),
30 multiple photons and metastable energy level rather than
meanwhile n represents the number denoting photons
31 energy transfer up-conversion process like inorganic ma-
absorbed in per up-converted process (often take the first
32 trix up-conversion materials of NaYF4:Yb3+/Er3+.38
integer more than n when n is not an integer). Figure 5
33 indicates the dependence of UC intensity on the laser
34 power: calculated n=1.98 and 1.01 for 540 nm and 651 nm
35 emissions respectively. These facts mean that populations
36 on states of 4S3/2 and 4F9/2 result from two-photons UC
37 processes at least. Due to the existence of the cross-
38 relaxation and nonradiative transitions in MOF, we can
39 deduce that the UC process results from multiphotons
40 absorption process of Er3+ and the exact number of pho-
41 tons is far more than 2.
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50 Figure 3. UCL of Up-MOF-Y1-χ/Erχ with different concen-
51 tration of Er3+ (range of χ is from 2% to 100%) with the
52 excitation at 980 nm.
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primary emissions at 520 nm (from 2H11/2 to 4I15/2) and

1 540 nm (from 4S3/2 to 4I15/2) which locate in green-light
2 region via radiative transition. Also, two near-infrared
3 photons may be absorbed sequentially by one Er3+ and
4 used to promote electronic population to high lying ener-
5 gy levels, and such excited state population finally emits
6 red light of 651 nm via the relaxation back to ground state
7 through the transition of 2H11/2→4S3/2→4F9/2→4I15/2. It is
8 possible that other excitation routes for level 4F9/2 derived
9 from the interactions of neighboring Er3+ exist.38 However
10 detailed investigation of such process is beyond the scope
11 of current work, and it can be explained by else published
12 study.43
13
14
15
16 Figure 5. Plot (ln-ln) of up-conversion intensity versus
17 excitation power (standard Up-MOFs-Y/Er).
18
19 To further understand the up-conversion mechanism of
20 Up-MOFs, we measure the absorption spectra of various
21 samples and the results are shown in Figure S4. The ab-
22 sorption spectra of various Up-MOFs exhibit a relatively
23 wide absorption band from ~960 nm to ~1150 nm which
24 should be caused by organic matrix and may further lead
25 to ligand-to-metal energy transition.41, 42 This observation
26 also demonstrates the existence of coordination bonds
27 between Er3+ and carboxyl from organic ligands.
28
29
30
31 Figure 7. Time evolution and single exponential fitting
32 curve of the green UCL (540nm) of standard Up-MOF-
33 Y/Er under pulse laser excitation at 980 nm.
34
35 To further demonstrate the up-conversion process, UCL
36 lifetime of the standard Up-MOFs-Y/Er at 540nm under
37 pulse laser excitation of 980 nm has also been measured
38 and plotted in Figure 7. Obviously, entire lifetime consists
39 of population curve and decay curve, suggesting that the
40 emission results from an up-conversion process. The de-
41 cay curve is well conformed to a single exponential func-
42 tion with the decay time of 133.89 μs, which is consistent
43 with the decay time of Er3+ in other up-conversion mate-
44 rials.44 Generally, up-conversion materials suffer from the
45 situation of low quantum efficiency because of the exist-
Figure 6. Up-conversion energy scheme of Er3+ from ing of a mount of nonradiative relaxation process and the
46 near-infrared excitation to visible emission.
47 susceptibility to complex dispersion environment. Hence,
48 we will particularly focus on enhancing up-conversion
Based on above analysis, the UC emission of Up-MOF- emission intensity in the further study.
49 Y/Er has been further demonstrated to be the excited
50 state absorption process in trivalent ions Er. A scheme of
51 CONCLUSIONS
up-conversion energy transfer process in Er3+-based MOF
52 is exhibited in Figure 6. Absorption at 980 nm is followed In summary, a series of metal organic frameworks with
53 by energy transfer to 4I11/2 energy level of Er3+. Subsequent- up-conversion luminescence under NIR excitation have
54 ly, second absorption leads to the population at a higher been successfully fabricated via a facile and simple one-
55 energy level of 2H11/2. By virtue of the nonradiative relaxa- step synthesis method. After being comprehensively
56 tion processes (2H11/2→4S3/2), absorbed photons lead to two characterized by a suite of measurements such as SEM,
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PXRD, PL and so on, it is demonstrated that Up-MOFs Transfer Biosensor (FRET) for Sensitive Detection of Lead Ions
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3 Wang, F.; Chi, D.; Hor, T. S.; Zhang, P.; Liu, G.; Han, Y.; Liu, X.
near-infrared light excitation of 980nm. Moreover, the
4 Enhancing Multiphoton Upconversion through Energy Cluster-
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5 and attributed to ESA. The fine-organized porosity and (10) Ai, K.; Zhang, B.; Lu, L. Europium-based Fluorescence
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17 ASSOCIATED CONTENT Wang, Y.; Wang, X.; Han, S.; Liu, X.; DuChene, J. S.; Zhang, H.;
18 Supporting Information. Chemicals and materials. Char- Zhang, Q.; Chen, X.; Ma, J.; Loo, S. C.; Wei, W. D.; Yang, Y.;
19 Hupp, J. T.; Huo, F. Imparting Functionality to a Metal-organic
acterization. Elemental analysis characterization of Up-
20 Framework Material by Controlled Nanoparticle Encapsulation.
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25 AUTHOR INFORMATION Properties in High Optical Quality Nano ZIF-8 Thin Films with
26 Tunable Thickness. J. Mater. Chem. 2010, 20, 7676-7681.
27 Corresponding Author (17) Liu, X.; He, L.; Zheng, J.; Guo, J.; Bi, F.; Ma, X.; Zhao, K.;
28 * E-mail address: libinteacher@163.com (B. Li) Liu, Y.; Song, R.; Tang, Z. Solar-Light-Driven Renewable Butanol
mahp@ciomp.ac.cn (H. Ma). Separation by Core-Shell Ag@ZIF-8 Nanowires. Adv. Mater. 2015,
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27, 3273-3277.
30 (18) Zhao, X.; Xiao, B.; Fletcher, A. J.; Thomas, K. M.; Brad-
31 ACKNOWLEDGMENT
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32 The authors greatly thank to the financial supports of the tion of Hydrogen by Nanoporous Metal-Organic Frameworks.
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