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A terbium metalorganic framework with stable

luminescent emission in a wide pH range that acts
as a quantitative detection material for
nitroaromatics
Jinzeng Wang,a Wei Sun,a Siyuan Chang,a Houting Liu,a Guonan Zhang,a
Yanqin Wanga and Zhiliang Liu*ab
Nitroaromatics are the principal components of explosives and infamous environmental pollutants in the
organic synthesis industry. Although high sensitivity towards the detection of nitroaromatics have been
demonstrated, selective and quantitative detection are critical for practical applications. Luminescent
MOFs constructed by d10 transition metal ions (Zn/Cd) and p-conjugated ligands for nitro aromatics
sensing have been widely reported, but the detection eciency is insucient due to the weak and
non-characteristic luminescence behaviours. And, luminescent MOFs constructed by lanthanide ions
which possess enhanced characteristic and strong luminescence emission for nitroaromatic detection

Received 9th April 2015

Accepted 26th May 2015

are rare. Herein, we report a uorescent MOF with stable emissions, [Tb(L1)2/3(L2)1/2(H2O)2]$2H2O (where
H3L1 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine, H2L2 terephthalic acid), whose characteristic

DOI: 10.1039/c5ra06308f

emission intensity can maintain more than 80% in a wide pH range (pH 410). Interestingly, this

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luminescent MOF can quantitatively detect nitroaromatics.

Introduction
It is known that nitroaromatics are the principal components of
explosives and infamous environmental pollutants in the
organic synthesis industry. Nitroaromatic compounds such as
nitrobenzene (NB), 4-nitrotoluene (4-NT), 2,4-dinitrotoluene
(2,4-DNT) and trinitrotoluene (TNT) and so on, are on the black
list of anti-terrorist or environment security in the USA, the
European Union and China, etc. Therefore, selective, quantitative and easily portable methods for detecting these kinds of
compounds are crucial. The instrumental analytical techniques
generally used for detecting nitro aromatics include gas chromatography coupled with mass spectrometry, Raman spectroscopy, energy dispersive X-ray diraction, and ion mobility
spectrometry (IMS), but these methods are generally expensive
and oen not easily portable. Due to the presence of electron
withdrawing nitro-group, nitroaromatic compounds can serve

College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot,

010021, P. R. China. E-mail: cezlliu@imu.edu.cn; Fax: +86-471-4992147; Tel: +8618686029088

Inner Mongolia Key Lab of Fine Organic Synthesis, Inner Mongolia University,
Hohhot, P. R. China
Electronic supplementary information (ESI) available: Crystallography details
and additional gures. X-ray crystallographic data for the structures of Tb-MOF
has been deposited with the Cambridge Crystallographic Data Center. CCDC
1056824. For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/c5ra06308f

48574 | RSC Adv., 2015, 5, 4857448579

as strong oxidants and interact with some conjugated electron

donors containing delocalized p electrons. Therefore, chemical
sensing methods based upon uorescence quenching are
feasible, and these methods are convenient and in high
demand for use in detection or sensing.1
The immense interest in designing of metalorganic
frameworks (MOFs) materials is of considerable increasing in
recent years due to their intriguing structural topologies and
potential applications in gas storage,2 drug delivery,3
heterogeneous catalysis,4 separation,5 proton conductively6
and chemical sensing.7 Recently, a large amount of luminescent MOF sensors exhibiting high selectivity and sensitivity for detecting anions,8 cations,9 explosives,10 small
molecules,11 and vapor12 have been reported. The ability of
luminescent MOFs to propagate the hostguest interaction to
detectable changes makes them promising candidates for
chemical sensor. As far as the luminescent MOFs for detecting nitroaromatics, most of which were constructed by d10
transition metal ions (Zn/Cd) and p-conjugated ligands.13
The pioneering work of Li et al. and others has demonstrated
the potential of luminescent MOFs in nitroaromatics detection.14 The uorescence of this kinds of MOFs is centered on
the organic linking group of the framework, and may be
assigned to pure intra-ligand emission. However, the detection eciency of previous reported luminescent MOFs is
insucient due to the weak and non-characteristic luminescent emission.

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It is well known that lanthanide metal ions have characteristic

luminescence emission when excited at a particular wavelength.
Although, the emission of lanthanide ions suers from weak light
absorption and the spin- or parity-forbidden ff transition, the
organic linker containing p-conjugated in lanthanide based MOFs
can act as antenna, which greatly enhance the lanthanide characteristic emission of the MOFs. Therefore, the lanthanide based
MOFs may be the potential candidates for chemical sensing.
Indeed, our research group and some others have reported a few
Eu3+/Tb3+ based luminescent MOFs for nitroaromatics detection.15
However, compared to d10 ions based MOFs, a few lanthanide
based luminescence MOFs acting as nitroaromatic compounds
sensing have been reported.16 Furthermore, lanthanide (e.g. Eu3+/
Tb3+) based MOFs have several advantages over d10 ions based
MOFs, including strong characteristic emission and readily
observed colour by the naked eye under a standard UV lamp.
Herein, we present the MOF [Tb(L1)2/3(L2)1/2(H2O)2]$2H2O,
denoted Tb-MOF (where H3L1 2,4,6-tris(4-carboxyphenoxy)1,3,5-triazine, H2L2 terephthalic acid). It displays a threedimensional (3D) open framework structure (see Fig. 1) with
relatively large channels hosting highly disordered guest (H2O)
molecules. Remarkably, we nd that Tb-MOF emits high bright
characteristic green light readily observed by the naked eye
under a standard UV lamp. Tb-MOF possesses relatively stable
luminescent properties in wide pH range. The luminescence of
Tb-MOF can be selectively and quantitatively quenched by
nitroaromatic compounds, indicating its possibility of being a
sensing material for nitroaromatics.

Experimental section
Materials and general characterizations
All reagents and solvents were used as received from commercial supplies without further purication. Fourier transform

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infrared (FTIR) spectra (KBr disk) were measured with a

TENSOR 27 FT-IR spectrophotometer. Elemental analyses for C,
H, N were obtained from a Perkin-Elmer 2400 elemental
analyzer. TGA were measured with NETZSCH TG 209 under
heating rate of 10  C min1. Powder X-ray diraction
measurements were recorded on a EMPYREAN PANALYTICAL
apparatus.
Synthesis of [Tb(L1)2/3(L2)1/2(H2O)2]$2H2O
A mixture of Tb(NO3)3$6H2O (0.2 mmol), 2,4,6-tris(4carboxyphenoxy)-1,3,5-triazine, (0.2 mmol), and terephthalic
acid (0.1 mmol) was dissolved in 10 mL of mixture solvent (5 mL
distilled water and 5 mL methyl cyanide) and adjusted the pH of
solution around 4.5 by NaOH solution. Then it was sealed in a
23 mL Teon-line stainless-steel autoclave and heated at 120  C
for 72 h followed by cooling to room temperature at the rate of
5  C h1. The resulting colorless block crystals were isolated
aer being ltered, washed with distilled water several times
and dried at ambient temperature; yield 75% (0.095 g) based on
Tb(NO3)3$6H2O. Anal. calc. for: C, 37.69%; H, 2.85%; N, 4.41%.
Found: C, 37.88%; H, 2.73%; N, 4.66%.
Single crystal X-ray diraction
For single crystal XRD measurements, a suitable crystal for the
compound was carefully selected under a polarizing microscope
and glued to a thin glass ber. The single crystal diraction data
were collected on a Agilent Xcalibur E X-ray single crystal
diractometer equipped with graphite-monochromatic Cu-Ka
radiation at 293 K. Empirical absorption corrections were
applied using the SADABS program.17 The structure of Tb-MOF
was solved by direct methods and rened anisotropically by fullmatrix least squares techniques on F2 values, using the SHELX97 program.18 Hydrogen atoms were added on appropriate
positions in theory and rened with isotropic thermal parameters riding on those parent atoms. All hydrogen atoms in the
coordination polymer were generated geometrically and rened
isotropically using the riding model. Crystallographic data and
structure renement parameters for Tb-MOF are listed in Table
S1. Selected distances and bond angles for Tb-MOF are listed
in Table S2.
Luminescence measurements method

(a) Ball and stick representation of the asymmetric structural

unit of the Tb-MOF. Symmetry codes: A: 1  y, 1 + x  y, z, B: x + y, 1
 x, z, C: z  y, 1 + x  y, z, D: 1  x + y, z  x, z, E: 1  x, 1  y, 1  z, F:
4/3  y, 1/3 + x  y, 1/3 + z, G: 2/3  x + y, 4/3  x, 1/3 + z. (b) The
rudder-like 3D structure with the coordinated water molecules
omitted (along the c axial) (left). 1D chain constructed by Tb3+.
Fig. 1

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The luminescence spectra for the powdered solid samples were

measured at room temperature on a Hitachi F-7000 uorescence
spectrophotometer. The excitation slit and the emission slit were
5.0 nm, PMT voltage 700 V. The scan speed is 240 nm min1.
The luminescence properties of Tb-MOF were studied in
solid states. To investment the sensing properties of Tb-MOF,
the ne grinding sample Tb-MOF (3 mg) were ultrasonic
agitated for 30 min then dispersed in various nitroaromatics
ethanol solution (5 mL) to form a stable emulsion at room
temperature.
The uorescence titrimetric method was used to measure
the concentration dependent luminescence intensity for TbMOF dispersed in nitrobenzene (NB) solutions. In this case,

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12 mg of Tb-MOF dispersed in 20 mL ethanol and the dierent

amount of NB was added in above suspension system.

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Results and discussion

A luminescent three-dimensional Tb-MOF, [Tb(L1)2/3(L2)1/2
(H2O)2]$2H2O, was synthesized solvothermally in mixture
solvent. Single crystal structure analysis reveals that Tb-MOF
 exhibiting a threecrystallized in the triclinic space group R3
dimensional framework. The asymmetric unit of Tb-MOF
contains one crystallographically independent Tb3+ ion, twothird of L13 ligand, half a L22 ligand, two coordinated H2O
molecules and two isolated solvent H2O molecules.
As depicted in Fig. 1, Tb3+ ion is eight-coordinated by two
oxygen atoms of one bidentate carboxylate groups from L13
ligand, four monodentate oxygen atoms from L13 and L22
ligands separately and two oxygen atoms from H2O molecules.
to 2.506(4) A,
the O
The TbO distances range from 2.271(4) A
TbO0 angels are between 52.91(12) and 151.95(15) . Selected
bond lengths and bond angles for Tb-MOF are listed in Table S2
(ESI). The L13 exhibits types of (a) and (b) coordination mode
separately as shown in Fig. 2, acting as sexadentate metal linker
and tridentate linker for the latter. The L22 exhibits series a
coordination mode and acts as tetradentate metal linker. For
the binuclear Tb3+ subunit, the Tb3+ are bridged by two-fold
carboxyl groups from L13 and L22 ligands one by one forming a one-dimensional chain along the b direction (Fig. 1). The
chains are connected by the carboxylic oxygen atoms of tridentate L13 ligands into a two-dimensional plane then further
bridged by the L13 and L22 ligands into a three-dimensional
framework. PLATON analysis indicates that the solvent acces 3 and 4.2%, respectively.
sible volume and porosity are 442.8 A
The structure can be simplied as a 3,3,3,3,5-connected
framework with the point Schlai symbol {103}{4 
102}3{4$82}3{42$83  105}3{83}, as shown in Fig. 3.
To reveal the thermal stability and further support the
molecular formula of the Tb-MOF, the TGA measurement was
performed on pure crystal samples of Tb-MOF under an N2
atmosphere with a heating rate of 10  C min1 over the range of
301100  C (Fig. 4). The compound shows favourable thermal
stability. The TGA curve shows two regions of weight loss. The
rst weight loss between 100140  C is 11.07%, which corresponds to the loss of two isolated water molecules and two
coordinated water molecules, calculated to be 11.29%. The
second weight loss, above 420  C, results from the decomposition of the compound. According to the TGA pattern analysis we
can conclude that, the isolated water molecules in the pores are
easily removed before 140  C, and in the range of 140420  C,
the compound remain intact aer the removal of the isolated
and coordinated water molecules (see Fig. S1 and S2).
Compared to the luminescence emission of as-made sample,
the slight red-shi of activated sample is due to the change of
Tb3+ energy levels caused by the loss of coordinated water
molecules (Fig. S2).
Exposed under the standard UV lamp (254 nm), the Tb-MOF
presents very strong green light which can be observed by the
naked eye. The solid-state luminescent spectrum of Tb-MOF

48576 | RSC Adv., 2015, 5, 4857448579

Fig. 2

Coordination modes of L13 and L22 in series (a) and (b).

Fig. 3

3D topology.

Fig. 4 The TG curve of Tb-MOF.

was recorded under ambient conditions. The high luminescence intensity of Tb-MOF mostly owes to the highly conjugated
structure of the organic linkers, which commonly known as
antenna eect and greatly enhances the optical performance
of the Tb3+ ions. The four characteristic emission bands are
located at 491 nm, 545 nm, 584 nm, 622 nm which attributed to
5
D47F6, 5D47F5, 5D47F4 and 5D47F3 transitions of Tb3+,
respectively, upon the excitation at 369 nm (Fig. 5).
The most prominent characteristic emission peak of TbMOF is presented at 545 nm which can be readily observed as
bright green light by the naked eye. The strong visible emission

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Fig. 5

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Excitation and emission spectra of Tb-MOF.

The luminescent intensity of Tb-MOF immersed in dierent pH

aqueous solutions.

Fig. 6

provides the possibility of Tb-MOF acting as a luminescence

sensor. It is noteworthy that Tb-MOF could keep high characteristic emission intensity in water when the pH value varied
from 4 to 10 (as shown the insert in Fig. 6, the characteristic
emission intensity can keep more than 80% in pH range of 4
10). From the evidence of PXRD, the framework of Tb-MOF
immersed in dierent pH also can stay stable (see Fig. S3).
Comparing to other chemical sensors,7c this signicant luminescent stability in wide pH range makes the Tb-MOF to be an
excellent candidate for luminescent sensor.
As a matter of fact, luminescent MOFs have several advantages for detecting organic small molecules.19 In this case,
MOFs are expected to be highly promising host for guest
molecules, and energy transfer between the host-MOFs and
guest molecules may produce a synergistic eect for the ecient identication of specic molecules. Thus, we have
analyzed the luminescence properties of Tb-MOF aer
immersed in dierent selected analytes. To explore the potential luminescence sensing ability of Tb-MOF, the ne grinding
samples were dispersed in common organic small molecule
solutions (such as the 0.1 mol L1 ethanol solution of methyl
cyanide,
trichloromethane,
DMF,
benzene,
toluene,

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nitrobenzene, m-dinitrobenzene and paranitrotoluene) and the

photoluminescent (PL) spectra were recorded to dierent analytes. As depicted in Fig. 7(a), the signicant quenching of
uorescence intensities were observed upon addition of TbMOF to nitroaromatic compounds containing solutions such
as NB, m-DNB and PNT. Accordingly, Fig. 7(b) presents a
megascopic uorescence quenching eect. Such observations
demonstrate the possibility of Tb-MOF for selective sensing of
nitroaromatic compounds. Based upon structure analysis, this
Tb-MOF shows a rigid, permanently porous structure which
contains conjugated aromatic rings within the ordered framework. Thus, the hostguest interaction can propagate between
Tb-MOF and aromatic compounds via pp interactions or
dipoledipole interactions. Thereby, the uorescence quenching mechanisms between the luminescent MOFs and the
nitroaromatics can be explained in previous reports of our
research group and some others.14a,d,15d
As shown in Fig. 8, the powder X-ray diraction (PXRD)
patterns of obtained samples are consistent with the corresponding single crystal simulated pattern which indicates the
good phase purity of Tb-MOF. To explore the lattice stability of
Tb-MOF aer immersed in analyte solution, the PXRD patterns
of Tb-MOF immersed in NB and m-DNB solution were measured
and the result indicates that the nitroaromatics loading only
very slightly impacts on the crystalline integrity of the Tb-MOF.
In order to investigate whether the second substituent group
of NB inuence the detection ability of Tb-MOF, some nitroaromatic compounds with dierent second substituent group
on aromatic ring have been examined with a concentration of
0.1 M analytes in ethanol. According to the experimental results
(Fig. 9), no matter what type of second substituent group (e.g.
electron donor or acceptor) is introduced on the benzene ring of

(a) Luminescence spectra of Tb-MOF in dierent solvents. (b)

The picture of Tb-MOF in dierent solvents under 254 nm UV-lamp.

Fig. 7

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Fig. 8 PXRD of Tb-MOF stimulated (black), as-made (red), after

immersed in m-DNB (blue), after immersed in NB (pink).

Fig. 9 The luminescence intensity of Tb-MOF dispersed in ethanol

solutions of dierent nitroaromatic analytes (m-DNB m-dinitrobenzene, 4-nitro CB 4-nitrobenzene chloride, PNT paranitrotoluene, NB nitrobenzene and 4-NP p-nitrophenol).

nitrobenzene, Tb-MOF shows obviously quenching eect

towards all selected nitroaromatic derivatives. Namely, Tb-MOF
is a potential excellent luminescence detection material for
most of the nitroaromatic compounds.
The photoluminescent (PL) spectrum of Tb-MOF dispersed
in EtOH exhibits strong emission at 545 nm when excited at
369 nm. To explore the ability of Tb-MOF to detect nitroaromatic compounds quantitatively, uorescence-quenching
titrations were performed with incremental addition of nitrobenzene (NB) as representative to Tb-MOF dispersed in EtOH.
High uorescence quenching was observed upon incremental
addition of NB solution. The visible bright green emission of
Tb-MOF vanished upon the addition of the NB solution, the
uorescence quenching by NB could be quantitatively determined at low concentrations. As depicted in Fig. 10, the
quenching of luminescence intensity of Tb-MOF displays an
ideal linear correlation with the increasing of the concentration
of NB (from 50 ppm to 1000 ppm). Furthermore, m-dinitrobenzene (m-DNB) was investigated, which also presents the
similar linear relationship of luminescence-quenching
(Fig. S4). The results provides us a feasible and promising

48578 | RSC Adv., 2015, 5, 4857448579

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Fig. 10 Concentration dependent luminescence for the Tb-MOF

dispersed in nitrobenzene (NB).

Recycling of Tb-MOF dispersed in NB. The luminescence was

recovered by washing with EtOH several times (intensity percentage
I/I0  100%).

Fig. 11

quantitative analytical approach to detect nitroaromatic

compounds by using luminescent Tb-MOF material as a
chemical sensor.
In addition, detection of NB with Tb-MOF can be fully
reversible. Aer quenching, the photoluminescence of Tb-MOF
can be recovered by simply washing the sample with ethanol (3
mg sample, 5 mL ethanol solvent was used under ultrasonic
washing condition for two minutes several times). As depicted
in Fig. 11, aer 5 time recycles, Tb-MOF showed almost identically rapid and evident responses to NB. The slight uorescence decay of the recovered Tb-MOF may be mainly caused by
the sample loss during the recycle experimental process.

Conclusions
In conclusion, a highly luminescent Tb-MOF, [Tb(L1)2/3(L2)1/2
(H2O)2]$2H2O, was designed and successfully synthesized. It is a
novel metalorganic material with stable uorescence emission
in wide pH range. Probably through electric charge transfers
luminescent quenching mechanism similar to that in the
previous reported systems, Tb-MOF can sense nitroaromatics

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based on luminescence quenching eect. Interestingly, the

visible bright green emission of Tb-MOF could be quantitatively
quenched upon the addition of the nitroaromatics at low
concentrations. Therefore, this luminescent MOF can quantitatively detect the nitroaromatics. Furthermore, such detection
was also proven to be reversible. These remarkable preliminary
results point to a new and important application of lanthanide
metalorganic framework materials. Comprehensive studies of
lanthanide luminescent MOFs are currently underway to
further explore their potential in nitroaromatics sensing. It can
be envisioned that one can develop a series of lanthanide
luminescent MOFs that will have highly sensitive and selective
responses towards a particular nitroaromatic compounds.

Acknowledgements
We would like to kindly acknowledge the NSFC (21361016) and
Inner Mongolia Foundation for Natural Science (2013ZD09)
nancial support.

Notes and references

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