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DOI: 10.1039/C8DT02329H

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Erbium(III)-Based Metal-Organic Frameworks with Tunable

Upconversion Emissions
Mengxue Li,‡a Salma Gul,‡a Dan Tian,‡a Enlong Zhou,a Yangbo Wang,a Yingdong Han,a Lisha Yin,*,a

Dalton Transactions Accepted Manuscript

Received 00th January 20xx,
Accepted 00th January 20xx Ling Huang*,a
DOI: 10.1039/x0xx00000x

www.rsc.org/

A series of lanthanide-based metal-organic frameworks (Ln-MOFs) by varying the target organic ligands used so that variable
with significantly improved and tunable upconversion emissions luminescence upconversion emissions can be obtained. Moreover,
were prepared. Y-MOF co-doped with Yb3+/Er3+ ions have exhibited the organic ligands used for Ln-MOFs construction could also be
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characteristic upconversion emissions at 520, 545, and 658 nm involved in energy transfer, which brings extra options as well as
under 980 nm laser excitation, the intensities of which vary with advantages for this type of materials towards luminescence tuning.
Yb3+/Er3+ concentrations. In addition, experimental results have In addition, the pores of Ln-MOFs can also accommodate light-
indicated that excited state absorption mechanism is responsible emitting guest molecules. These features could facilitate the
for the upconversion process of Y-MOF:Yb/Er materials. This study synergistic reactions between Ln-MOF and luminescent lanthanide
has provided a novel design principle and experimental basis for ions, which will further expand the applications of such light-emitting
preparation of luminescent Ln-MOFs materials. materials.
On the other hand, some remarkable characteristics that MOF
Metal-organic frameworks (MOFs)1 with characteristics of easy possesses, such as facile synthesis, stable structure, structural and
synthesis, periodic 3-dimensional (3D) porous network, together functional diversity, as well as adjustable distances of metal ions by
with structural and functional diversity have been proved to be a varying organic ligands, are expected to complement the drawbacks
promising and versatile family of crystalline porous materials.2,3 that lanthanide-doped upconversion nanoparticles have, such as
MOFs have integrated the advantages of both organic and inorganic tedious synthesis procedures, low yields, rigid crystal lattices, and
materials and drawn great research enthusiasms in the past two small light absorption co-efficiency. Thus, this work aims to extend
decades. Among the large number of MOFs, lanthanide MOFs (Ln- the design strategy of lanthanide-doped inorganic luminescent
MOFs) has remained fascinating due to their highly similar nanomaterials to Ln-MOFs (Scheme 1). Particularly, Y-MOF is
coordination environment with gradually varied ionic radius.4 selected as the host material which could be co-doped with specific
Various Ln-MOFs have been used for the sensing and detection of lanthanide ions to realize upconversion luminescence.
cations/anions and small molecules because of its quick response,
excellent sensitivity, and high selectivity.5,6 However, the
luminescence of most Ln-MOFs reported to date are excitated by the
ultraviolet light, which has prevented its applications from
biosensing and bioimaging due to the weak penetrability, harmful
irradiation, and autofluorescence interference from biological
tissues.7 Therefore, it is vital to prepare Ln-MOFs that can generate
visible luminescence via energy upconversion mechanism, and
especially excited by near-infrared light.
Different from lanthanide-doped upconversion nanoparticles
where the lattice constants of host materials are usually fixed with
certain chemical composition and crystal structure,8 Ln-MOFs
possess highly periodic porous structures that can be widely adjusted

a. Institute
of Advanced Materials (IAM), Jiangsu National Synergetic Innovation
Center for Advanced Materials (SICAM), Nanjing Tech University (NanjingTech), 30
South Puzhu Road, Nanjing, 211816, China. E-mail: [email protected]; Scheme 1 Schematic illustration of the Ln-MOFs design strategy.
[email protected]
‡
These authors contribute equally.
†Electronic Supplementary Information (ESI) available: Crystallographic detail These Y-MOFs co-doped with Yb3+/Er3+ ions at varied
(CIF), supplementary table, structural figures and PXRD, TGA, IR characterizations. concentrations have exhibited adjustable and characteristic

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upconversion emissions at 520, 545, and 658 nm under 980 nm laser accessible volume is 26.8% (1340.1 Å3) per unit cell (5008.0 ÅOnline
View Article
3), as

excitation. Furthermore, the luminescence upconversion mechanism estimated using PLATON. 11 DOI: 10.1039/C8DT02329H
in Ln-MOFs has been discussed and attributed to excited state A series of new compounds 1-5 and 7-9 are obtained when
absorption.9 Y(NO3)3·6H2O, Yb(NO3)3·5H2O, and Er(NO3)3·6H2O were added at
Single-crystal structure analysis have revealed that different molar ratios into the synthesis system. Powder X-ray
{[(Er0.6Yb0.9)(bptc)(BDC)0.25(H2O)(CH3OH)]·(H2O)0.5}n (6) crystallizes in Diffraction (PXRD) patterns (Fig. S3) indicate that the crystal
the orthorhombic space group Ibam and possesses a 3D framework structures of compounds 1-5 and 7-9 are maintained upon mixed
containing two crystallographically independent Yb3+/Er3+ ions. Due doping ions owing to the same coordination environment of Y3+, Er3+,
to the similar coordination environment of lanthanide ions, the and Yb3+, which are in good agreement with the simulated patterns
metal position may be simultaneously occupied by Er3+ and/or Yb3+ based on the X-ray single-crystal data. The slight shift of the

Dalton Transactions Accepted Manuscript

ions in compound 6. Therefore, the ionic ratio in the crystal structure diffraction peaks may be caused by the lanthanide contraction
is confirmed by ICP (Table S1). As shown in Figs. 1 and 2, Yb3+/Er3+1 is effect.12 Furthermore, the ionic ratios of Y3+/Yb3+/Er3+ in these
coordinated by six carboxylate oxygen atoms from four bptc4- ligands compounds were confirmed by ICP analysis (Table S1). The almost
and two oxygen atoms from one water molecule and one CH3OH. identical IR spectra of these Ln-MOFs (Fig. S4) clearly suggests that
Yb3+/Er3+2 is surrounded by four carboxylate oxygen atoms from two the framework of these compounds is not affected when co-doped
bptc4- ligands, and four carboxylate oxygen atoms from two 1,4- with lanthanide ions.
dicarboxybenzene ligands (Figs. 1 and 2). The neighboring Ln···Ln
distance spanned by the bptc4- ligand is 6.629 Å. In addition, 2,2’-
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carboxylate groups of bptc4- ligands adopt the µ2-η1:η1 bidentate

mode (Fig. S1a), while 5,5’-carboxylate group exhibits bidentate
chelating coordination mode. Moreover, the Yb3+/Er3+1—O and
Yb3+/Er3+2—O in 6 show different bond lengths (Fig. S1b and S1c).
The dihedral angles (Fig. S1d) between the two benzene rings of
bptc4- ligand in compound 6 are 68.7o. The Er−O bond lengths
(2.242−2.740 Å) are all within the normal range.10

Fig. 2 Comparison of coordination environment of Yb3+/Er3+1 (a) and

Yb3+/Er3+2 (b) in compound 6.

Thermogravimetric analysis profiles (Fig. S5) indicate that the

first weight loss at temperature range of 70–194 °C corresponds to
the loss of water molecules, and then the organic framework
collapsed at the temperature range of 329–600 °C.
The upconversion behavior of compound 3 (Er-MOF) was first
studied under 980 nm laser excitation where three major emission
peaks at 520, 545, and 658 nm were observed (Fig. 3). As is well
known, when absorbed 980 nm photons, Yb3+ ions in the classical
NaYF4:Yb/Er nanoparticles could sensitize Er3+ ions by transferring
energy in its 2F5/2 energy level to that of the 4I11/2 of the neighbouring
Er3+ ions.13 Herein, we expect that similar energy transfer could also
occur in the organic-inorganic hybrid materials, namely Ln-MOFs.
Generally speaking, luminescence of Ln-MOFs can be produced from
Fig. 1 (a) The coordination environment of Yb3+/Er3+ ions in 6. (b)
lanthanide ions, organic ligands, charge transfer between ligands and
Schematic view of the 3D framework of 6 along the c-axis. (c) Space-filling
metal ions, or energy transfer between the host framework and
view of the 3D framework of 6 along the b-axis. (d) Schematic illustration
guest molecules.14-16
of topology of the 3D network.
Firstly, Er-MOF (3) and a series of Y-MOF:Yb/Er at varied Y/Yb/Er
Furthermore, every bptc4- ligand in 6 is connected by four eight- molar doping ratios of 0/95/5 (4), 0/70/30 (5), 0/50/50 (6), 30/60/10
coordinated Yb3+/Er3+1 ions and one eight-coordinated Yb3+/Er3+2 (7), 30/50/20 (8), 30/40/30 (9) were prepared to study the effect of
ion, which results in a 3D porous framework structure (Figs. 1b and Yb3+ ion concentration on the characteristics of the upconversion
1c). From the topological perspective, bptc4- ligand could be luminescence emissions by measuring the luminescence spectra of
simplified as a five-connected spacer (Fig. S2a), and each Yb3+/Er3+1 these compounds in the powder state. The results indicate that Y-
ion connecting four L4- ligands could be regarded as a four-connected MOF:Yb/Er samples with varied Yb3+/Er3+ doping concentrations
node (Fig. S2b). Besides, each Yb3+/Er3+2 ion connected with two L4- exhibit the same emission profiles (Fig. 3). Comparison of the
ligands and two 1,4-dicarboxybenzene ligands could also be seen as photoluminescence spectra has suggested that Er-MOF (3) gives the
one 4-connected node (Fig. S2c). Finally, these simplifications give strongest emission among all the compounds. When Yb3+ ions are co-
rise to a three-dimensional 4,4,5-connected topological network (Fig. doped in Er-MOFs, the luminescence intensity of Ln-MOFs 4, 5, and
1d). After removing solvent molecules filling in the pore, the 6 increases at increased Yb3+ doping concentration. In addition, when

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Y3+ and Yb3+ ions were co-doped, the luminescence intensities of 658 nm emission (137 μs) was found in 30 mol% (compound View Article5)Online
Er3+
compound 7, 8, and 9 are mainly related with the Er3+ concentration doped-MOFs (Fig. S7, Table S2). These results are consistent with the
DOI: 10.1039/C8DT02329H
but are all weaker than those without Y3+ (compounds 3-6). Based on decay time of Er3+ in previous reports.22 In terms of the upconversion
these results and the larger Ln···Ln distance (6.629 Å) in the Ln-MOFs luminescence intensity improvement, though these Y-MOF:Yb/Er
crystal lattice, we infer that the upconversion mechanism of Y- only show upconversion emissions caused by excited state
MOF:Yb/Er presumably follows the excited state absorption of Er3+ absorption of Er3+ ion, we anticipate that the proposed Ln-MOFs
ions by the interaction between multiple photons and metastable design strategy could not only offer a fresh platform for developing
energy levels, rather than the energy transfer upconversion new upconversion materials, but also provide novel insights into the
processes usually found in NaYF4:Yb/Er inorganic upconversion functionalization of this class of crystalline materials.
nanoparticles.17 The larger Ln···Ln distance (6.629 Å) has exceeded

Dalton Transactions Accepted Manuscript

the optimal Ln···Ln distance (ca. 3.5 and 3.3 Å, Fig. S6) in the crystal
structure of the classical hosts, such as NaYF4 and Sc2O3,8a,18 which
may count against the efficient energy transfer between Yb3+ and Er3+
ions. In lanthanide doped inorganic upconversion nanoparticles,
energy transfer can be easily realized when the distance between
lanthanide ions is within 3~4 Å.19
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Fig. 4 Log-Log plots of the upconversion emission intensity against the excitation
power of 980 nm laser for compound 3 (a), 4 (b), and 9 (c). Luminescence decay
curves of compounds 3, 4, 5, and 6 at 545 nm (d) under 980 nm excitation.
Fig. 3 Photoluminescence spectra of powder-state compounds 3-9 under 980 According to the above analysis, the emissions of compounds 3,
nm laser excitation. 4, 9 all follow a two-photon upconversion process. Therefore, the
To further investigate the underlying mechanism of Y-MOF:Yb/Er, luminescence of these compounds originates from Er3+ ions and
3 typically designed powder-state compounds 3 (Er-MOF), 4 (Y/Yb/Er possesses the same upconversion mechanism. Fig. 5 illustrated the
= 0/95/5), and 9 (Y/Yb/Er = 30/40/30) were chosen to determine the proposed upconversion energy transfer pathways where upon 980
emission power dependence at 545 and 658 nm (Fig. 4a-c), which nm laser excitation, electrons of Er3+ ions absorb the pumping
obeys the following relationship,20,21 photons and get excited from the ground state of 4I15/2 to that of 4I11/2,
𝐼𝐼𝑢𝑢𝑢𝑢 ∝ 𝑃𝑃 𝑛𝑛 which was further populated to the 2H11/2 energy level by absorbing
where Iup is the upconversion emission intensity, P is the pumping
power, and n represents the number of pumping photons to produce
an upconverted photon. The slopes n obtained in compounds 3 (Er-
MOF), 4 (Y/Yb/Er = 0/95/5), and 9 (Y/Yb/Er = 30/40/30) are 1.829,
1.144, and 1.783 for 545 nm and 1.210, 1.656, and 1.783 for 658 nm
emission, respectively, indicating that both emissions follow a two-
photon upconversion process. Therefore, we infer that the
upconversion emission can be attributed to an excited state
absorption process on account of nonradiative transitions and cross-
relaxation of MOFs.9
The upconversion emission decay curves at 545 and 658 nm of Y-
MOF:Yb/Er powders were also measured (Fig. 4d), which can be
represented by the 4S3/2 →4I15/2 and 4F9/2 → 4I15/2 energy transfer of
Er3+ ions for compounds 3 (Er-MOF), 4 (Y/Yb/Er = 0/95/5), 5 (Y/Yb/Er
= 0/70/30), and 6 (Y/Yb/Er = 0/50/50). The decay curve at 545 nm
agrees with two exponential function, in which the decay times of
compounds 3, 4, 5, and 6 are 225, 301, 271, and 280 μs (Fig. 4d),
respectively. The longest lifetime (301 μs) was found in 5 mol% Fig. 5 Energy upconversion pathways of Er3+ ions in Y-MOF:Yb/Er under 980
(compound 4) Er3+ doped-MOFs for 545 nm emission, while that of nm laser excitation.

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a second photon, and meanwhile the non-radiative relaxation from 7. S., Zhang, W. Shi, P. Cheng, M. J. Zaworotko, J. Am. Chem.
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Dalton Transactions Accepted Manuscript

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We thank the Natural Science Foundation of China (21601086, Mater. Chem. Phys., 2012, 135, 317-321.
21371095), the Natural Science Foundation of Jiangsu Province 18. Y. Pan, X. Xie, Q. Huang, C. Gao, Y. Wang, L. Wang, B. Yang, H.
(BK20160994, BK20170968, BL2014015), and the International Su, L. Huang, W. Huang, Adv. Mater., 2018, 30, 1705256.
Postdoctoral Fellowship Program funded by China Postdoctoral 19. J. Wang, R. Deng, M. A. MacDonald, B. Chen, J. Yuan, F. Wang,
Science Foundation (20170012) for financial support. We thank D. Z. Chi, T. S. A. Hor, P. Zhang, G. Liu, Y. Han, X. Liu, Nat. Mater.,
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Conflicts of interest 21. Y. Wang, T. Wei, X. Cheng, H. Ma, Y. Pan, J. Xie, H. Su, X. Xie,
L. Huang, W. Huang. J. Mater. Chem. C, 2017, 5, 3503-3508.
There are no conflicts to declare.
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L. Gu, L. Huang, Dalton Trans., 2018, 47, 4950-4958; (b) X. Cheng,
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