Materials Letters 126 (2014) 189192

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

A luminescent terbium metal-organic framework for selective sensing

of nitroaromatic compounds in high sensitivity
Wei Sun, Jinzeng Wang, Houting Liu, Siyuan Chang, Xiaoting Qin, Zhiliang Liu n
College of Chemistry and Chemical Engineering, Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University,
Hohhot 010021, Inner Mongolia, China

art ic l e i nf o

a b s t r a c t

Article history:
Received 5 March 2014
Accepted 8 April 2014
Available online 16 April 2014

A novel luminescent terbium metal-organic framework [Tb(HL)(H2O)4]
H2O (1) has been successfully
prepared by the facile hydrothermal reaction of Tb(NO3)3
6 H2O and the -conjugated ligand H4L
(H4L 1,10 -biphenyl-2,3,30 ,50 -tetracarboxylic acid). Single crystal structure analysis reveals that 1 exhibits
a 2D layered structure. The solid sample of 1 emits high bright green light which can be readily observed
by the naked eye when excited at 288 nm at ambient temperature. Interestingly, the luminescence of
ne grinding 1 particles dispersed in ethanol can be selectively and sensitively quenched by nitroaromatic compounds, which indicates that 1 is a potential luminescent sensory material for nitro explosives.
& 2014 Elsevier B.V. All rights reserved.

Keywords:
Nitroaromatic compounds
Selective sensing
Metal-organic frameworks
Crystal structure
Luminescence

1. Introduction
In recent years, designing functional metal-organic framework
(MOF) materials has attracted considerable attention, because of
their interesting structural topologies [1] and the extensive applications they embodied in catalysis [2], drug delivery [3], selective
sensing [4], and so on. Among the various applications, selective
molecule sensing properties seems interesting and fascinating.
So far, a large number of MOFs have been reported for their
sensing properties, especially the luminescent MOFs. The sensing
function of luminescent MOFs was applied to recognize metal
cations [5], anions [6], and small organic molecules [7].
Considering the fact that nitroaromatic compounds are both
environment pollutional small molecules in the black list of
priority pollutants [8] and explosive threating to public security
[7], their rapid and trace detection is crucial to environmental
protection and homeland security. Compared to other reported
explosive detection technologies, such as gas chromatography
coupled with mass spectrometry, some reported new detection
methods based on luminescence quenching of MOFs are inexpensive, simpler and sensitive [9]. Due to the presence of electron
withdrawing nitro-group, nitroaromatic compounds can serve as
strong oxidants and interact with some electron donor conjugated
polymers containing delocalized electrons. So designing a
luminescent MOF with the electron-rich ligand and proper metal
ion is critical for its use as detecting nitroaromatics.

Corresponding author. Tel.: 86 471 4995414; fax: 86 471 4992147.

E-mail address: cezlliu@imu.edu.cn (Z. Liu).

http://dx.doi.org/10.1016/j.matlet.2014.04.042
0167-577X/& 2014 Elsevier B.V. All rights reserved.

So far, most of reported luminescent MOFs for nitroaromatic

compounds sensing are constructed by Zn/Cd ions and conjugated ligands [10,11], and the luminescence bands of which
are non-characteristic or weak. However, to date, the luminescence MOFs for nitroaromatic compounds sensing based on
enhanced characteristic luminescence of rare earth ions have been
rarely reported [12]. Herein, we report a new 2D layered Tb(III)
MOF (1) which exhibits high selectivity and sensitivity towards
nitroaromatic compounds. We select H4L as a -conjugated ligand
(Scheme S1 in ESI) and Tb(III) ion as the metal connector due to its
high afnity to carboxylates and nondetrimental nature to uorescence. Moreover, because of the lanthanide-centered emission
can be sensitized by electron conjugated systems with efcient
energy-transfer (so called antenna effect), the solid sample of 1
emits high bright green light which can be readily observed by the
naked eye when excited at 288 nm at ambient temperature. The
luminescence of 1 can be selectively and sensitively quenched by
nitroaromatic compounds, indicating its possibility of being a
luminescent sensory material for nitro explosives.

2. Experimental
A mixture of Tb(NO3)3
6H2O (0.2718 g, 0.6 mmol), H4L
(0.099 g, 0.3 mmol), NaOH (4 drops, 1 mol/L) and water (12 ml)
was sealed in a 25 ml Teon-lined stainless vessel and heated at
120 1C for 72 h. After being cooled to room temperature, the white
rod-like crystals were obtained. Yield of 40% based on Tb
(NO3)3
6H2O. (CCDC reference number 988819). IR (KBr pellet,
/cm  1): 437(m), 658(w), 692(m), 765(s), 1254(m), 1382(s), 1448

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W. Sun et al. / Materials Letters 126 (2014) 189192

(s), 1549(s), 1609(w), 1656(w). Elemental Anal.(%) Calcd for: C,

33.35, H, 2.97; Found: C, 33.36, H: 2.96.

3. Results and discussion

[Tb(HL)(H2O)4]
H2O crystallizes in monoclinic space group
P21/n. Each asymmetric unit consists of one terbium ion, one
HL3  anion ligand, four coordinated water molecules and an
isolated solvent water molecule. The nine-coordinated terbium
ion exhibits a distorted tricapped trigonal prism geometry completed by ve carboxyl oxygen atoms of the HL3  ligand and four
oxygen atoms of the coordinated water molecule (Fig. 1(a)). TbO
distances range from 2.361(5) to 2.565(5) , the O  Tb  O0
angles are in the range of 51.47(2)151.21(2)1 (see Table S2 for
selected bond lengths and angles). Each HL3  ligand connects
three Tb(III) ions acting in bidentate-chelating and monodentate
coordination modes. All the metal centers are further connected
via the carboxylic oxygen atoms of HL3  ligands to construct an
undulated 2D layered framework (Fig. 1(b)).
The thermal gravimetric analysis curve of 1 displays an initial
weight loss of 13.16% (calculated: 15.61%) in the range of 100
250 1C probably attributed to loss of ve water molecules (coordinated and lattice) (see Fig. S1). The major mass loss occurs in the
temperature range of 250800 1C with the loss of 37.25% corresponding to the decomposition of the compound.
The solid-state luminescence spectra of 1 was investigated
upon excitation at 288 nm under ambient temperature, which
exhibits four characteristic peaks of Tb (III) (5D4-7F6: 492 nm,
5
D4-7F5: 546 nm, 5D4-7F4: 580 nm, and 5D4-7F3: 623 nm) (Fig.
S2). It is well-known that the luminescence of terbium cation has a
low molar absorptivity and that the ff transitions are spin and
parity-forbidden. However, it has been shown that the lanthanidecentered emission can be sensitized by electron conjugated
systems with efcient energy-transfer, which is known as the
antenna effect. The most prominent line in 1 is presented at
546 nm which can be readily observed as bright green light by the
naked eye. The strong visible emission provides the possibility of 1
acting as a luminescence sensor.
To explore the potential luminescence sensing properties of 1,
the ne grinding sample 1 was dispersed in common organic small
molecule solvents such as MeOH, EtOH, MeCN, DMF, isopropanol
(IPA), benzene (BZ), toluene (TO), chlorobenzene (ClBZ) and nitrobenzene (NB) (see Fig. 2(a)). As depicted in Fig. 2(a) and (c), the

signicant quenching of uorescence intensity was observed upon

addition of aromatic ring containing molecules such as TO, ClBZ
and NB and the most important one is NB. Such observations
demonstrate the possibility of 1 for selective sensing of nitroaromatics. Fig. 2(b) shows that the PXRD patterns of obtained samples
are consistent with the corresponding simulated pattern which
indicates the good phase purity of 1. The PXRD pattern of 1 and
NB-immersed 1 suggests that the basic framework remains in the
process of sensing NB.
Three reasons may account for the quenching effect of 1
towards NB. (1) There exists a competition of absorption of the
excitation wavelength energy between carboxylate ligand and NB
(see Fig. S3). Thus the energy delivered by the carboxylate ligand
to Tb3 ion could be decreased signicantly, quenching the
luminescence of Tb3 in response [8]. (2) There are - interactions between NB molecules and frameworks, during which the
NB with electron-withdrawing groups serves as electron acceptor
and frameworks in 1 can be regarded as electron donor. So the
photoinduced electron transfers from the benzene rings of the
ligands to the NB and the uorescence quenching behavior was
observed [12]. (3) All the MOF particles could be dispersed well in
the analyte solution when being measured. The surface of the
crystals absorbs most part of the excitation energy. Thus the
excitation radiation cannot reach the inner crystals completely
and signicant electron transfer takes place from the framework
to NB on the surface of the MOF particles [13]. In this case, the
quenching effect occurs on the surface of the crystals.
The signicant quenching of luminescent intensity shows that
1 is likely to be a good luminescence sensor for NB. So the further
investigation was done for examining the relationship of luminescence quenching degree with the concentration of NB (Fig. 3(a)). 1
was dispersed in ethanol as the standard suspension, and then the
NB concentration in ethanol was gradually increased to monitor
the emissive response. It turns out that the luminescence intensity
gradually decreased with increasing content of NB. The luminescence spectra with emission intensity of 1 was completely
quenched when the concentration of NB reached 769 ppm
(5 mM), indicating the extremely high sensitivity towards NB.
Meanwhile, the 1 particles could be regenerated and reused for
several cycles through centrifuging and washing the solid sample
several times (Fig. S4).
In order to explore whether the substituent groups of NB
inuence the sensor ability of 1, some mononitro-aromatic compounds have also been examined with a concentration of 1 mM in

Fig. 1. (a) Coordination environment of Tb3 in 1 (symmetry codes, A:  x 3/2, y1/2, and  z 3/2; B: x  1/2,  y 3/2, and z  1/2). Hydrogen atoms and one solvent
water molecule are omitted. (b) The undulated 2D layered structure with the coordinated water molecules omitted (along the c axial) and its corresponding simplied
uninodal 5-connected net of (33.43.54) topology.

W. Sun et al. / Materials Letters 126 (2014) 189192

191

Fig. 2. (a) Luminescence spectra of dispersed 1 in various pure solvents under ex 288 nm. (b) The power X-ray diffraction (PXRD) patterns: simulated from single-crystal
diffraction data (bottom), as-synthesized 1 (middle) and NB-immersed 1 (top). (c) Photograph of 1 (3 mg) in different solvents under the UV lamp (EX at 254 nm).

Fig. 3. (a) Luminescence spectra of dispersed 1 in different NB concentrations (05 mM) in ethanol under ex 288 nm (the inset shows corresponding emission intensities
(em 546 nm) of 1 in different NB concentrations). (b) Luminescence intensity of 1 in different analytes at room temperature. Grinded crystals of 1 (3 mg) were dispersed in
an ethanol solution of different analytes (1 mM, 5 ml). NB (nitrobenzene), 3-NP (m-nitro phenol), 4-nitro BA (BAbenzoic acid), 2-NP (o-nitro phenol), 4-NP (p-nitro
phenol), 4-NT (NT nitrotoluene), and 4-nitro CB (CB chlorobenzene).

ethanol (Fig. 3(b)), according to the experimental results, 1 shows

more obviously quenching effect towards mononitro-aromatic
derivatives than NB, which shows that 1 is a potential excellent
luminescence sensor material for nitroaromatic explosives. In the
meantime, 2-NP, 3-NP and 4-NP show different quenching effects
demonstrating the impact of their electron density.

Acknowledgments
Financial supports by the NSFC (21361016) and Inner Mongolia
Autonomous Region Foundation for Natural Science (2013ZD09)
are kindly acknowledged.

Appendix A. Supporting information

4. Conclusion
In summary, a luminescent 2D layered Tb-MOF [Tb(HL)(H2O)4]

H2O (1) was designed and synthesized by the hydrothermal method
with the -conjugated ligand. The dispersed solution of 1 in ethanol
shows selective and remarkable quenching effect in the luminescence emission to various solvent molecules. Meanwhile, with a high
sensitivity to NB in this work, the Tb-MOFs with electron rich
frameworks can be explored as potential luminescence sensing
materials for detecting nitroaromatic explosives.

Supplementary data associated with this article can be found in

the online version at http://dx.doi.org/10.1016/j.matlet.2014.04.042.
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