DOI: 10.1002/cphc.
201200265
Microwave-Assisted Modular Fabrication of Nanoscale
Luminescent Metal-Organic Framework for Molecular
Sensing
Weiting Yang, Jing Feng, Shuyan Song, and Hongjie Zhang*[a]
Miniaturizing the size of metal-organic framework (MOF) crys-
tals to the nanometer scale is challenging, but it provides
more advanced applications without changing the characteris-
tic features itself. It is especially useful to investigate the corre-
lation between the porous properties and the interfacial struc-
tures of nanocrystals. Using amino acids as capping agents,
nanoscale Tb-MOF-76 is fabricated rapidly by means of micro-
wave-assisted methods. Both the modular effects of the
amimo acids and the acid–base environment of the reaction
1. Introduction
Metal-organic frameworks (MOFs) are a class of hybrid materi-
als constructed from the limitless choice of metals and organic
bridging ligands. Their well-defined porosity and tunable
chemical functionality make them good candidates for gas
storage, separation, heterogeneous catalysis, and sensing.[1–9]
Miniaturizing the size of MOF crystals to the nanometer scale
offers an interesting approach to design functional nanomate-
rials for biological and biomedical applications, because their
compositions can be systematically tuned by the judicious
choice of building blocks. For example, specific non-toxic
porous iron carboxylate nanoMOFs are well suited to serve as
nanocarriers for the efficient controlled delivery of challenging
antitumoural and retroviral drugs against cancer and AIDS.[10]
Nanoscale gadolinium MOF materials are used as potential
multimodal contrast-enhancing agents.[11] However, only a few
approaches for the nanometer-sized MOFs fabrication have
been developed, including the reverse microemulsion,[11–13] the
microwave assisted synthesis[14] and the coordination modula-
tion method using capping agents.[15–17] The fabrication of
nanoscale MOF materials with outstanding properties by
a rapid and effective method is of great importance.
The lanthanide MOFs (Ln-MOFs), an important member of
the MOF family, have received great attention, due to their rich
coordination characteristics and exceptional optical and mag-
netic properties arising from their 4f electrons.[18–23] Numerous
Ln-MOF structures have been reported by a judicious selection
of organic ligands and inorganic molecular building blocks
(formed in situ), but potential application studies based on
their luminescence are rare.[24–28] Chen et al. reported on Ln-
MOFs with terminal organic solvents for recognizing and sens-
ing anions,[25] with open metal sites for sensing small mole-
cules,[26, 27] and with Lewis-basic sites for recognizing and sens-
ing metal cations.[28, 29] Recently, they utilized a mixed Ln-MOF
ChemPhysChem 0000, 00, 1 – 6  2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
medium have an important impact on the morphologies and
dimensions of Tb-MOF-76. The structures of the samples are
confirmed by powder X-ray diffraction, and the morphologies
are characterized by SEM. Photoluminescence studies reveal
that these Tb-MOF-76 materials exhibit a green emission corre-
sponding to the transition 5D4 !7FJ of Tb3 + ions under UV-light
excitation, which is sensitive to small organic molecules in so-
lution.
as a luminescent thermometer.[30] However, the Ln-MOF materi-
als they used were mostly bulk crystals, restricting their appli-
cation in biology and biomedicine to some extent. Herein, we
report on the microwave-assisted method combined with the
use of amino acids as capping reagents for the synthesis of
nanoscale Tb-MOF-76 exhibiting recognition of acetone mole-
cules.
2. Results and Discussion
2.1 Morphologies of Tb-MOF-76
Proline, which possesses only one carboxylic group compared
to the organic ligand 1,3,5-benzenetricarboxylic acid (H3BTC),
was chosen to modulate the coordination sphere on Tb.
Figure 1 shows the SEM images of Tb-MOF-76 crystals synthe-
sized by adding various amounts of proline (0–4.0 mmol). In
the absence of proline, the crystals are pillar-like rods with
lengths of 30  10 mm. The addition of the capping agent pro-
line leads to a dramatically decrease in crystal size. For exam-
ple, the addition of 0.3 mmol proline reduced the length of
the crystals to around 5.0 mm. Increasing the amount of added
proline to 0.5 mmol, micro crystals of 0.2  1.0 mm were ob-
tained. Rod-like monodisperse nanocrystals with dimensions of
[a] Dr. W. Yang, Dr. J. Feng, Dr. S. Song, Prof. Dr. H. Zhang
State Key Laboratory of Rare Earth Resource Utilization
Changchun Institute of Applied Chemistry
Chinese Academy of Sciences
Changchun, 130022 (China)
Fax: (+ 86) 431-85698041
E-mail: hongjie@ciac.jl.cn
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/cphc.201200265.
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 H. Zhang et al.

was raised from 5.90 to 6.86. However, further addition of pro-

line to 4.0 mmol did not affect the pH value any more (Table 1,
entries 6 and 7). This observation can be explained by the iso-
electric point of proline which is at 6.3. These results indicate
that not only the capping agent content affects the crystal
growth, but the pH also plays a key role.
The structures of the resulting samples were further studied
by powder X-ray diffraction (PXRD), as shown in Figure 2.
PXRD studies indicated that the particles are highly crystalline

Figure 1. SEM images of Tb-MOF-76 crystals synthesized with addition of

proline: a) 0, b) 0.3, c) 0.5, d) 1.0, e) 2.0 and f) 4.0 mmol.

50  15 nm in width and 100  25 nm in length were formed Figure 2. Simulated and experimental powder X-ray diffraction patterns of
when the amount of proline was increased to 1.0 mmol. With Tb-MOF-76 with addition of different amounts of proline.

2.0 mmol of proline, aggregation of rod-like nanocrystals was

obtained. Further increasing the amount of proline did not
lead to any further obvious changes in the morphology of the
product. These experiments reveal that with an increase in the
amount of proline, the crystal size is firstly dramatically de-
creased and then kept almost unchanged. The role of proline
in reducing the crystal size is attributed to its modulating
effect on the coordinating interactions between the lanthanide
ions and organic linkers.
On the other hand, other factors could also have an effect
on the crystal size. Therefore, the synthesis conditions were
studied in detail. As shown in Table 1, the pH value of the reac-
tion mixture gradually increased with the addition of proline,
accompanied by the conspicuous decrease in crystal size.
When 2.0 mmol of proline were added, the pH of the mixture
and of the same structure as Tb-MOF-76.[31] Meanwhile, com-
pared to the simulated spectrum of the single-crystal structure,
the broader X-ray diffraction peaks reveal that the size of the
particles is markedly decreased.
Glycine was also tested as a capping agent in order to mod-
ulate the morphology of Tb-MOF-76. Similar to proline, the in-
crease of glycine led to a decrease in crystal size (Figure 3).
However, in contrast to proline, here the capping agent con-
tent was limited, as glycine is poorly soluble in the mixture of
dimethylformamide (DMF) and H2O and the minimal crystal
size was reached at 1 mm. The structure of the as-synthesized
samples were confirmed by PXRD and are shown in the Sup-
porting Information (Figure S1, Supporting Information).

2.2 IR Spectra
Table 1. Change in pH value of the reaction mixture with the addition of
proline. IR spectroscopy was used to characterize the functional groups
[a]
in bulk and in the nanocrystals (see Figure S2 in the Support-
Entry Proline [mmol] Initial pH Final pH
ing Information). Both samples exhibited the characteristic
1 0 3.98 4.88 asymmetric stretching vibrations of carboxylate groups in the
2 0.2 4.95 5.06
3 0.3 4.97 5.26 range of 1580–1440 cm1 and the symmetric vibrations cen-
4 0.5 5.29 5.44 tered at 1382 cm1.[32–34] Interestingly, in comparison with the
5 1.0 5.58 5.72 nanocrystals, bulk crystals exhibited two distinct bands, cen-
6 2.0 5.90 6.86 tered at 1573 and 1543 cm1, in the asymmetric stretching-vi-
7 4.0 6.0 7.0
bration range of the carboxylate groups. These two bands are
[a] The reaction mixtures of 0.1 mmol Tb(NO3)3, 0.1 mmol BTC, 10 mL superposed in the nanocrystals, which is tentatively ascribed
DMF and 2 mL H2O were kept unchanged.
to the overlap of the asymmetric vibrations stemming from

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Nanoscale Luminescent Metal-Organic Framework

Figure 4. Excitation (g) and emission spectrum (c) of Tb-MOF-76 a in

Figure 3. SEM images of Tb-MOF-76 crystals synthesized with addition of ethanol (excited and monitored at 298 and 544 nm, respectively).
glycine : a) 0.3, b) 0.5, c) 1.0 and d) 2.0 mmol.

the carboxylate groups of the surface-coordinated proline and

BTC. However, the superposition could also originate from the
stretching vibrations of benzene rings, as well as from the de-
formation vibrations of water molecules, which are located in
the same wavenumber range.[34]

2.3 Luminescent Sensing Properties

The basic structural features of MOF-76 are the one-dimension-
al channels of about 6.6  6.6 2 along the [001] direction, in
which the terminal solvent molecules partially occupy the
pores.[31] Its characteristic photoluminescence (PL) allowed the
material to be used for sensing molecules.[26, 27] To further study Figure 5. 5D4 !7F5 transition intensities of nanoscale Tb-MOF-76 a dispersed
the sensing properties in solution, the smallest particles syn- in various pure solvents when excited at 298 nm.
thesized herein, with dimensions of 100 nm, were chosen for
luminescent characterization. The nanoparticles of Tb-MOF-76
were treated at 120 8C under high vacuum for 16 h to obtain
the evacuated nanoparticles (Tb-MOF-76 a). 2 mg of the as-
evacuated samples were then dispersed in 3 mL ethanol using
ultrasonification to form a suspension. The photoluminescence
spectra of Tb-MOF-76 a are shown in Figure 4. Compound Tb-
MOF-76 a exhibited the characteristic transitions of the Tb3 +
ion at 488, 544, 581 and 620 nm, which are ascribed to the
5
D4 !7F6, 5D4 !7F5, 5D4 !7F4, and 5D4 !7F3 transitions, respec-
tively.
To examine the potential of Tb-MOF-76 a for sensing small
molecules, its photoluminescent properties in common solvent
suspensions were investigated. As shown in Figure 5, the
5
D4 !7F5 transition intensities of the emission spectra are large-
ly dependent on the solvent molecules, especially in the case Figure 6. Emission spectra of Tb-MOF-76 a ethanol suspension in the pres-
of acetone, which showed a significant quenching effect. Such ence of various contents of acetone (excited at 298 nm). The inset shows
the luminescence change after the addition of acetone on Tb-MOF-76 a
solvent-dependent quenching behaviour is of interest for the under UV light.
sensing of acetone molecules, and thus it was examined in
detail. Nanoparticles of Tb-MOF-76 a were dispersed in ethanol
as the standard suspension, while the acetone content was almost disappeared at an acetone content of 5.0 vol %. The
gradually increased to monitor the emissive response. As emitted visible green light of the Tb-MOF-76 a suspension con-
shown in Figure 6, the luminescent intensity of the suspension taining acetone is significantly darker than the original one
significantly decreased with the addition of acetone, and it under UV light (Figure 6), which allowed us to identify the

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presence of small amounts of acetone in solution. The decreas-
ing trend of the luminescent intensity of the 5D4 !7F2 transi-
tion of Tb3 + at 544 nm versus the volume ratio of acetone
could be well fitted with a first-order exponential decay (Fig-
ure S3 in the Supporting Information), indicating that lumines-
cent quenching of Tb-MOF-76 a by acetone is diffusion-con-
trolled.[26]
In the solvents we used, acetone has a wide absorbing
range from 225 to 325 nm, while the other solvents have no
absorption at 298 nm. As mentioned above, the absorption
band of BTC is located between 250 and 310 nm, which is
overlaid by the absorbing band of acetone. Combined with
the absorption and luminescent spectra, it was suggested that
the energy absorbed by BTC is transferred to the acetone mol-
ecules, resulting in a decrease (even quenching) in PL intensity
of Tb-MOF-76. The quenching mechanism is consonant with
that proposed by Chen et al.[27]
3. Conclusions
In summary, nanoscale Tb-MOF-76 was synthesized by means
of microwave-assisted methods using amino acids as capping
agents. These materials exhibited characteristic Tb3 + ions pho-
toluminescence in solution, which is a sensitive sensor for ace-
tone molecules. It is expected that this easy access to lumines-
cent MOFs with a variety of terminal solvents and pore struc-
tures will render this strategy very practical and useful in ex-
ploring luminescent microporous small molecular sensors.
Experimental Section
Syntheses
Nanocrystals of Tb(BTC)(DMF)(H2O) (BTC = 1,3,5-benzenetricarboxy-
late) were prepared with the coordination modulation method. In
a typical synthesis, a solution of Tb(NO3)3·6 H2O (0.1 mmol), H3BTC
(0.1 mmol), proline (0–4.0 mmol) or glycine (0.3–2.0 mmol), dime-
thylformamide (DMF) (10 mL) and H2O (2 mL) was placed in
a 30 mL microwaves-transparent vial. 200 W of microwave power
was applied for 5 min to increase the temperature to 80 8C, then
keeping this temperature for another 30 min to crystallize nano-
scale Tb(BTC)(DMF)(H2O). After natural cooling to room tempera-
ture, the particles were isolated by centrifugation and washed sev-
eral times with DMF and ethanol to remove any unreacted reac-
tants, then dried in air.
Characterization
Powder X-ray diffraction (PXRD) patterns were performed on a D8
Focus (Bruker) diffractometer (continuous, 40 kV, 40 mA). The mor-
phologies of the samples were inspected using a scanning electron
microscope (SEM, S-4800, Hitachi). IR measurements were obtained
using a Bruker TENSOR 27 Fourier transform infrared spectrometer.
Samples were diluted with spectroscopic KBr and pressed into pel-
lets. The excitation and emission spectra were obtained with a HI-
TACHI F-4500 spectrophotometer equipped with a 150 W xenon
lamp as the excitation source. Absorption measurements were car-
ried out using a Shimadzu UV-3600 spectrophotometer.
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H. Zhang et al.
Acknowledgements
This work was supported by the National Natural Science Foun-
dation of China (Grant Nos. 21071140 and 21001100), National
Natural Science Foundation for Creative Research Group (Grant
No. 20921002) and China Postdoctoral Science Foundation
(Grant No. 20110491327).
Keywords: lanthanides · luminescence · metal-organic
frameworks · nanostructures · sensing
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Received: March 26, 2012
Published online on && &&, 2012

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ARTICLES
W. Yang, J. Feng, S. Song, H. Zhang* Quenched by acetone: Nanostructural
Tb-MOF-76 is synthesized by a micro-
&& – &&
wave-assisted method using amino
Microwave-Assisted Modular acids as capping agents. Its characteris-
Fabrication of Nanoscale Luminescent tic Tb3 + ion emission can be used as
Metal-Organic Framework for a highly sensitive means of detection
Molecular Sensing for acetone molecules (see picture).

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