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A first Ln−MOF as a trifunctional luminescent probe for efficient

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sensing of aspartic acid, Fe3+ and DMSO
Received 00th January 20xx,
Accepted 00th January 20xx Dongdong Yanga, Liping Lu*a, Sisi Fengab, Miaoli Zhu*ab
DOI: 10.1039/x0xx00000x
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Five 3D network Ln3+ metal−organic frameworks (Ln-MOFs) formulated as [[Ln(μ6-H2cpboda)(μ2-OH2)2]·xH2O]n [Ln3+ = La3+
(1), Nd3+ (2), Sm3+ (3), Eu3+ (4), Tb3+ (5), H5cpboda =5,5'-((5-carboxy-1,3-phenylene)bis(oxy))diisophthalic acid]) have been
synthesized via hydrothermal method. They have been established by single-crystal X-ray and powder diffraction analyses,
elemental analysis (EA) and thermogravimetric analyses (TGAs). All compounds are isostructural with three-dimensional
structures of the point symbol of (413·62)(48·66·8) in topology and crystallize in monoclinic space group P21/n. Interestingly,
the solid-state luminescence of complexes 4 and 5 show intense red and green emissions, respectively. Besides, the Tb-
MOF (5) is a good luminescent sensor not only to detect aspartic acid and Fe(III) ions with good stability, high efficiency
and reversibility but also to exhibit rapid response and high selectivity to DMSO. To our knowledge, it is the first Ln−MOF
as a luminescent probe for efficient sensing of DMSO, while the lone pair of electrons in the O of DMSO attacked the
positive charge at the protonation carboxylic acid of H5cpboda. Consequently, Tb-MOF (5) is a rare and versatile
fluorescent probe to aspartic acid, Fe3+ cations and DMSO simultaneously.

Introduction Dimethyl sulfoxide (DMSO), one of the sulfur-containing

In recent years, metal–organic frameworks (MOFs) have drawn
great attention in the sensing materials due to their rapid response
and outstanding selectivity and simple of the way.1-8 Compared to
transition metals, some of lanthanide-based MOFs (Ln-MOFs) have
been especially attractive owing to not only their intrinsic
luminescent characteristics of lanthanide ions, high colour purity,
excellent luminescence quantum yields and prolonged lifetime 9-10,
but also their properties such as easy manipulation, sensitivity, high
stability and rapid response. Especially for Eu3+ and Tb3+ ions, they
are widely used to synthesize sensing luminescent materials due to
their strong red and green emissions.12 Obviously, Ln-MOFs can be
used as potentially fluorescent probes.
Amino acids and iron ions are indispensable in our bodies to
maintain the necessities of living organisms. Fe 3+ is not only an
important component of hemoglobin, but also plays a key role in
the immune, enzyme systems and transcription of proteins.13-14
However, excess of Fe3+ can cause damage of organs like the
kidneys and heart.15 Among the many amino acids, aspartic acid is
one of common amino acids, which could bring about epilepsy,
stroke, even Lou Gehrig’s diseases.16 Hence, it is very important to
detect Fe3+ and aspartic acid sensitively and rapidly in human
health.
aInstituteof Molecular Science, Key Laboratory of Chemical Biology and Molecular
Engineering of the Education Ministry, Shanxi University, Taiyuan, Shanxi 030006,
People’ s Republic of China. luliping@sxu.edu.cn.bKey Laboratory of Materials for
Energy Conversion and Storage of Shanxi Province; Shanxi University, Taiyuan, Shanxi
030006, People’s Republic of China. miaoli@sxu.edu.cn
compounds, can not only be a common organic solvent but also as
a protective agent that reduces cell freezing and ice crystal
formation to reduce cell damage.17 However, DMSO can interact
with proteins to cause protein denaturation, which causes damage
to the liver and kidneys of the human body. Therefore, it is
important to design the suitable fluorescent probe to identify the
DMSO.
In recent years, a variety of Ln−MOFs as luminescent probes have
been applied for the detection of different analytes, including
organic anions, metal cations and some organic small molecules. 18-
22 However, few investigations focused on the highly sensitive
sensing of the aspartic acid and DMSO solvent based on
luminescent Ln-MOFs. Thus, it is still a great challenge to obtain a
target Ln-MOF to sensing of the aspartic acid and DMSO solvent
with high selectivity, sensitivity and stability.
Based on the above discussion, a series of lanthanide
functionalized Ln-MOFs formulated as [[Ln(μ6-H2cpboda)(μ2-
OH2)2]·xH2O]n [Ln3+ = La3+ (1), Nd3+ (2), Sm3+ (3), Eu3+ (4), Tb3+ (5)] have
been synthesized by the hydrothermal reaction of lanthanide ions
and 5,5'-((5-carboxy-1,3-phenylene)bis(oxy))diisophthalic acid
(H5cpboda). All products reveal the similar 3D (413·62)(48·66·8)
topological structure. Interestingly, the Tb-MOF shows high
selectivity and stable response to aspartic acid, Fe3+ ion and DMSO.
As we known, it is the first example of the luminescent probe based
on a Ln-MOF for sensing DMSO.
Experiment
Materials and methods.
H5cpboda was purchased from Jinan Henghua Trading Company in
China. All solvents and Ln(NO3)3·6H2O in the present work were

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available from commercial sources and without further purification.
A Bruker TENSOR27 spectrometer to measure FT-IR and it was
recorded from KBr pellets in the range of 4000–400 cm−1.
Thermogravimetric data (TGA) were gotten using Dupont thermal
analyzer in range of RT–800 °C under nitrogen flow with a heating
rate of 10 °C min−1. Powder X-ray diffraction (PXRD) data were
recorded on a Bruker D8 Advance X-ray diffractometer with Cu Kα
radiation (λ = 1.5418 Å) and the data were recorded within the 2
range of 5–50°. Elemental analyses of compounds were performed
using a Perkin-Elmer 240 elemental analyzer. The fluorescence
spectra were measured on a Varian Cary Eclipse Fluoromax-4
Spectrofluorometer with a xenon arc lamp as the light source. …
The Commission International de l'Eclairage (CIE) color coordinates
were calculated on the grounds of the international CIE standards.
Luminescence lifetime measurements were carried out on a
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Quantaurus-Tau Compact Fluorescence Lifetime Spectrometer
C11347.
Synthesis of complexes 1−5.
All complexes were synthesized in the similar method except for
the different starting lanthanide salts. A mixture of H5cpboda (48.2
mg, 0.1 mmol), Ln(NO3)3·6H2O (0.15 mmol) [Ln3+ = La3+ (1), Nd3+ (2),
Sm3+ (3), Eu3+ (4), Tb3+ (5)], CH3CN (3 mL), H2O (6 mL) and HNO3(1
mol/L, 0.3 mL) was placed in a Teflon reactor (25 mL) and heated at
140 °C for 72 h. Then naturally cooled down to room temperature,
the block-shaped crystals of complexes 1 - 5 were received. Washed
several times with distilled water and dried in air.
[[La(μ6-H2cpboda)(μ2-OH2)2]·1.382H2O]n (1). Yield 63% relative to
La. Anal. Calcd. (C23H17.76LaO15.38): C 40.67, H 2.61. Found: C 40.58, H
2.63. IR (KBr, cm−1): 3440s, 1678s, 1540s, 1383s, 1289m, 1137m,
1078m, 905w, 779m, 703w, 579w.
[[Nd(μ6-H2cpboda)(μ2-OH2)2]·1.372H2O]n (2). Yield 68% relative to
Nd. Anal. Calcd. (C23H17.74NdO15.37): C 40.31, H 2.59. Found: C 40.28,
H 2.62. IR (KBr, cm−1): 3446m, 1672s, 1540s, 1386s, 1286m, 1140m,
1013m, 911w, 776w, 700w, 603w.
[[Sm(μ6-H2cpboda)(μ2-OH2)2]·1.307H2O]n (3). Yield 68% relative to
Sm. Anal. Calcd. (C23H17.61O15.31Sm): C 40.08, H 2.55. Found: C 40.01,
H 2.58. IR (KBr, cm−1 ): 3446m, 1678m, 1550s, 1384s, 1289w,
1144m, 1018m, 911w, 773m, 707w, 600w.
Scheme 1 The synthesis strategy of Ln-MOFs 1–5
2 | J. Name., 2012, 00, 1-3
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[[Eu(μ6-H2cpboda)(μ2-OH2)2]·1.216H2O]n (4). Yield 68% View relative to
Article Online
Eu. Anal. Calcd. (C23H17.52EuO15.26): C 40.03, DOI: 10.1039/D0DT00938E
H 2.54. Found: C 40.01,
H 2.56. IR (KBr, cm−1): 3440(m), 1678(m), 1547(s), 1383(s), 1282(m),
1131(m), 1014(m), 905(w), 770(m), 707(w), 603(w).
[[Tb(μ6-H2cpboda)(μ2-OH2)2]·H2O]n (5). Yield 68% relative to Tb.
Anal. Calcd. (TbC23H17O15): C 39.87, H 2.46. Found: C 39.78, H 2.51.
IR (KBr, cm−1): 3446m, 1672m, 1622m, 1552s, 1389s, 1137m,
1024m, 905w, 773w, 604w.
X-ray crystallography
Dalton Transactions Accepted Manuscript
Crystallographic data of compounds 1-5 were collected on a
Bruker D8-Quest diffractometer equipped with a Photon 100
detector, with a graphite monochromator Mo-Kα radiation (λ =
0.71073 Å) at room temperature. SADABS23 was applied for
absorption corrections. Structures of complexes 1-5 were solved by
the direct methods using the SHELXS-2014 program24 and refined
on F2 with the full-matrix least-squares technique using SHELXL-
2016 program.25 The structures were solved through direct
methods and refined by full-matrix least-squares refinements based
on F2. After all non-H atoms were refined anisotropic thermal
parameters, hydrogen atoms attached to C atoms were added in
ideal positions and refined by a riding model. The selected bond
distances and angles of all complexes are listed in Table S1.
Results and discussion
Structural descriptions of Ln-MOFs 1-5
The single crystal X-ray diffraction data show that complexes 1-5
are isomorphism and crystallize in the monoclinic system with the
space group P21/n. Complexes 1 – 5 display also similar IR spectra in
the range of 4000–400 cm−1 based on their similar structural
characteristics (Fig. S1). The peaks at 3450–3440 cm-1 are the
stretching vibrations of O—H bonds in water and –COOH. The
bands from 1680 to 1380cm-1 correspond to the COO- symmetric
stretching vibrations, 1289–1130 cm-1 for COC symmetric stretching
vibrations. In addition, the peaks at 911–700 cm-1 were assigned to
the bending frequencies of O—C=O. Therefore, only the structure
of complex 5 (Tb-MOF) is described here in detail as a
representative.
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Table 1 Crystal data and structure refinement for complexes 1–5

1 2 3 4 5

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CCDC 1956547 1956548 1956549 1956550 1956551
Formula [C23H15LaO14]·1.382H2O [C23H15NdO14]·1.372H2O [C23H15SmO14]·1.307H2O [C23H15EuO14]·1.216H2O [C23H15TbO14]·H2O
Mr 679.17 684.31 689.25 690.01 692.28
Crystal Monoclinic Monoclinic Monoclinic Monoclinic Monoclinic
system
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space P21/n P21/n P21/n P21/n P21/n

group
T (K) 296 (2) 296(2) 296(2) 296(2) 296(2)
Size 0.25×0.25×0.2 0.3×0.25×0.24 0.30×0.25×0.24 0.28×0.25×0.25 0.30×0.20×0.20
a (Å) 11.1270 (8) 11.0859 (9) 11.0358 (8) 11.0093 (6) 10.9945 (7)
b (Å) 16.8656 (12), 16.7946 (11) 16.7709 (11) 16.7313 (9) 16.7248 (11)
c (Å) 13.2685 (9) 13.1735 (10) 13.1223 (9) 13.0739 (8) 13.0563 (8)
 (°) 90 90 90 90 90
β (°) 112.292 (2) 112.1255 (19) 112.0471 (17) 112.0393 (14) 112.027 (1)
 (°) 90 90 90 90 90
V (Å3) 2303.9 (3) 2272.1 (3) 2251.1 (3) 2232.2 (2) 2225.6 (2)
Z 4 4 4 4 4
Dx/mg 1.958 2.001 2.034 2.053 2.066
m−3
μ (mm-1) 1.94 2.37 2.70 2.90 3.26
Rint 0.056 0.066 0.061 0.062 0.052
GOF 1.05 1.10 1.02 1.03 1.09
F000 1343 1355 1360 1362 1360
R1 [I > 0.044 0.046 0.041 0.043 0.032
2σ(I)]
wR2 [I > 0.072 0.110 0.064 0.060 0.064
2σ(I)]
Δρmax 0.84 1.06 0.71 0.99 1.21
(eÅ−3)
Δρmin -0.65 -0.91 -0.88 -0.90 -0.61
(eÅ−3)

As shown in Fig. 1a, the asymmetric unit of complex 5 contains
one unique Tb(III) atom, one partial protonation ligand
(H2cpboda3-), two coordinated H2O molecules and one free H2O
molecule. Each Tb3+ ion is eight-coordinated by oxygen atoms
exhibiting a distorted {TbO8} geometry (Fig. 1b), and oxygen atoms
are derived from six H2cpboda3- ligands (O1, O2i, O6ii, O7iv, O9v,
O11iii), and two H2O molecules (O13, O14). The Tb–O bond lengths
and O—Tb—O bond angles are in the ranges of 2.302(4) to 2.468(5)
Å and 68.11(13)º-150.01(13) º, respectively, which is comparable to
those reported similar compounds.26-27 As shown in Fig. 1c, each
H2cpboda3- ligand links six Tb(III) ions with a μ5-η1:η1:η1:η1:η1:η1
coordination mode, and the four carboxylates of the H2cpboda3-
ligand adopt two different coordination modes (η1:η0, η1:η1), with
the distance of adjacent Tb3+ ions of 5.4829(3) and 5.5394(4) Å,
respectively. The Tb(III) ions are connected by carboxylates to form
a 1D chain, and the 1D chains are bridged by H2cpboda3- ligands to
form a 2D layer structure (Fig. 1c). The adjacent layers are jacked up
by H2cpboda3- ligands coordinated to Tb(III) ions to give rise to a 3D
coordination framework (Fig. 1d).
To gain a better insight into the nature of the 3D Ln-MOF
structure, the topological method TOPOS program28 was employed.
As shown in Fig. 1e, each H2cpboda3- ligand acts as a 6-connected
node and each Tb(III) ion also act as 6-connected node. Thus, the
structure can be simplified as a 6,6-connected net, which is a new
topological net with point symbols (413·62)(48·66·8) (Fig. 1e).
PXRD patterns and thermal analysis
PXRD patterns of complexes 1−5 are also carried out room
temperature to check the purity. As shown in Fig. S2, most peak
positions in simulated and experimental patterns are consistent,
demonstrating the phase purity of the bulk sample. The thermal
stabilities of complexes 1–5 were characterized by TGAs from RT to
800 °C at the heating rate of 10 °C min−1 under a N2 atmosphere

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(Fig. S3) and their thermal decomposition curves are also similar. Thus, View Article Online
DOI: 10.1039/D0DT00938E

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Fig. 1 (a) Perspective view showing the coordination environment of the Tb(III) ion in 5, symmetry codes: i -x+1, -y, -z+1; ii x+1/2,
-y+1/2, z+1/2; iii x-1/2, -y+1/2, z+1/2; iv -x+3/2, y-1/2, -z+1/2; v -x+2, -y, -z+1 (b) The 2D structure of complex 5. The inset is the
local coordination geometry of the Tb3+ ion of complex 5. (c) Three-dimensional network structure with channels. (d) The
topological network of complex 5.

we took complex 1 as a representative to analyse their thermal
stability (Fig. S3). The weight loss of complex 1 in the range of 65–
250°C is a total loss of 8.91%, which corresponds to the release of
two coordinated H2O molecules and the solvent H2O molecule
(calcd 8.96%). And the network of this compound presents a
plateau until approximately 400°C. Then the framework undergoes
decomposition in the range of 400–800 °C.
Photoluminescent properties.
As shown in Fig. S4, under the irradiation of ultraviolet light,
complexes 4 and 5 shows intense visible red and green fluorescence,
respectively. The solid-state luminescence spectra of complexes 1-5
and H5cpboda were measured at ambient temperature. For 1, the
emission spectrum shows a weak band at 412 nm under the
excitation at 325 nm (Fig. 2a), which may be due to the emission of
ligand-to-metal charge transfer (LMCT). The complexes 2 and 3
don’t show characteristic emission bands, which indicates that the
energy absorbed by the ligand cannot be transferred to the excited
state of the Ln(III) ion.
The emission spectrum of complex 4 (Figure. 2b) showed four
typical Eu3+ emissions. The one at 593 nm is distributed to magnetic
dipolar 5D0 → 7F1, more intense than that of the emission at 613 nm
which is from the electric dipolar 5D0 → 7F2 transition. The two
emission peaks at 650 and 698 nm are assigned to the 5D0 →7F3 and
5D → 7F transitions, respectively.
0 4
For 5, it exhibits characteristic Tb3+ peaks at 489, 543, 587and
620 nm, corresponding to the 5D4 → 7Fj (j = 6, 5, 4, 3) transitions,
respectively (Fig. 2c). Among the emission lines, the strongest
intensity of emission at 543 nm is attributed to the 5D4 → 7F5
transition.

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Fig. 2 Solid-state emission spectra of complexes. (a) 1 (λex = 325 nm), (b) 4 (λex = 370 nm), (c) 5 (λex = 335 nm) at room
temperature.

Sensing of organic solvent molecules.
We studied the fluorescence properties of complexes 1, 4 and 5
in these common organic solvents. The samples of complex 1, 4 and
5 (2.0 mg) were dispersed in 5.0 mL of different organic solvents
(dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), N,N-
dimethylformamide (DMF), methanol, ethanol, dichloromethane,
acetonitrile, acetone and aqueous solution), then treated by
ultrasonication for 30 min before the luminescence measurements.
As shown in Figures 3, S5 and S6, the complex 1 and 4 displays a
weak luminescence in common organic solvents and no fixed peak
shape. Compared with complex 1 and 4, 5 has stronger emission
intensity in organic solvents and excellent solvent stability of 5
prompt us to evaluate the suitability of 5 for sensing applications. In
complex 5. Furthermore, to explore the solvent and pH stability of
the complex 5, then soak the sample of complex 5 in different
organic solvents and pH for 24 hours, and then the samples were
recollected by centrifugation and air-drying before PXRD
measurement. The patterns conform with the theoretical ones,
which suggests 5 has good solvent stability (Fig. S7and S8). The
various organic solvents display different effects on the emission of
Tb-MOF, and the Tb-MOF exhibited the weakest emission in
acetone. It is worth noting the Tb-MOF exhibits a much higher
emission band in DMSO than that in other solvents.

Fig. 3 (a) Luminescence spectra and (b) intensities of the 5D4 → 7F5 transition for 5 dispersed in various organic solvents (5 mL, 2
mg 5). The inset is the corresponding photographs under UV-light irradiation at 365 nm.

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Fig. 4 (a) Emission spectra of complex 5 dispersed in different content DMSO/H2O mixed solvent and the change of the CIE
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chromaticity diagram with increasing DMSO content (left); (b) Linear fitted curve of the changes of DMSO/H2O with increasing
DMSO content.
In order to better understand the fluorescence properties of Tb-
MOF, it is very necessary to do the detection of different content
DMSO in aqueous solution. As shown in Fig. 4a, we found that the
fluorescence intensity of Tb-MOF enhanced obviously with the
increment of DMSO content in aqueous solution. The colour of the
system varies from green to yellow-green. In addition, we can see
that when the volume fraction of DMSO increases to close to 100%,
the fluorescence intensity is the strongest and the fluorescence
intensity of the DMSO/H2O (100%) is higher 18.85 times than that
of DMSO/H2O (0.0%). Moreover, the values of DMSO/H2O exhibit a
good linear relationship with DMSO in the volume fraction. The
linearity can be fitted as a function as follow:29
I/I0 = 0.1970VDMSO/H2O -0.4410 (1)
The I0 is the initial luminescence intensity, and I is the
luminescence intensity after the addition of the DMSO content. The
calculated values of the correlation coefficient (R2) is 0.9914, and
the limit of detection (LOD) for DMSO is calculated as 1.68% based
on eq (2):
3S B
LOD 
S (2)
The SB is standard deviation from five blank measurements for
H2O solution, and the S is the slope of the linear relationship in the
inset of Fig. 4b. The result indicates that complex 5 could be a good
fluorescent probe to detect DMSO in aqueous solution.
Sensing of amino acid
Secondly, considering good luminescent properties of complex 5,
we have found that the Tb-MOF can also be used for detection
amino acids in water. A 10 mg of the complex 5 is dispersed in 40
mL distilled water and treated by ultrasonication for 30 min to form
uniform suspension. Then the suspensions were respectively added
100 of µL (1.0 × 10-3 M) aqueous solution included different amino
acids (L-cysteine (Cys), L-leucine (Leu), L-glycine (Gly), L-
phenylalanine (Phe), L-threonine (Thr), L-tyrosine (Tyr), tryptophan
6 | J. Name., 2012, 00, 1-3
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(Try), L-isoleucine (Iso), L-histidine (His), L-valine (Val), L-proline
(Pro), L-glutamic acid (Glu) and L-aspartic acid (Asp)) to study its
selectivity and detection of amino acids at room temperature. As
illustrated in Fig. 5, compared to other amino acids, glutamic acid
showed less pronounced quenching and the aspartic acid has
obvious annihilation on the fluorescence intensity of Tb-MOF. Thus,
the Tb-MOF can also be seen as a promising luminescence probe for
sensing of aspartic acid among amino acid.
In order to understand the sensitivity of 5 as a luminescent
sensor of aspartic acid, the relationship between the concentration
of the aspartic acid and the luminescence intensities of the Tb-MOF
was studied. A 5 mg of complex 5 was dispersed in 10 mL of distilled
water forming uniform suspension, and then aspartic acid (1.0 × 10-
3 M) was gradually added to the suspensions. As shown in Fig. 6,
with an increasing of aspartic acid, the luminescent intensities
gradually decreased. This luminescence quenching can be
calculated by the Stern–Volmer equation: I0/I = 1+ Ksv [M]30-31 (I0 is
the emission intensity of Tb-MOF prior; I is the emission intensity
after adding the aspartic acid; [M] is the concentration of the
analytes). The Stern–Volmer plots for aspartic acid are almost linear
at low concentrations, with a correlation coefficient of 0.9956. The
Ksv value of 9.80×103 M−1 indicates the remarkable influence of
aspartic acid on quenching the emission of 5 (Fig. 6b). By a ratio of
LOD = 3σ /m we calculated the limit of detection (LOD) for aspartic
acid, where σ for standard deviation for Tb-MOF calculated from
five blank measurements and m for slope of the linear curve for
plotted Tb-MOF at lower concentration. The detection limit of the
Tb-MOF system for probing aspartic acid was 7.95×10−6 M. The
sensing ability of the Tb-MOF systems is comparable to those of
previously reported MOFs for detection of aspartic acid (Table S1).
Further, we investigated the influence on the system of mixed
amino acids. As shown in Fig. 7, there is no significant effect of
other amino acids on the luminescence quenching caused by
aspartic acid.
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Fig. 5 (a) Luminescence spectra and (b) intensities of the 5D4 → 7F5 transition for 5 dispersed in different amino acid

Fig. 6 (a) Luminescence responses of 5 (10.00 mg dispersed in 40.00 mL of water) toward different concentrations of aspartic acid in water
(inset: the colour change of the solution (TOP)). (b) Plot of the KSV curve between the luminescence intensity of aspartic acid. (inset: Stern–
Volmer plots of analytes)
Sensing of metal cations
Third, we also have investigated the potential of complex 5
toward detecting different metal cations. Hence, we chose various
cations (Na+, K+, Ag+, Zn2+, Cd2+, Mn2+, Ca2+, Mg2+, Co2+, Ni2+, Fe2+,
Cu2+, Cr3+, Fe3+) ) to investigate the recognition performance of
complex 5. After addition of 100 μL (1×10-3 M) of each cation to the
same suspensions, interestingly, fluorescence intensity is almost
completely quenched in sample containing Fe3+ cation (Fig. 8), and
some cations (Fe2+, Cu2+ and Cr3+) showed less pronounced
quenching and other metal cations showed minor decrease of the
luminescence intensity. Thus, the Tb-MOF acts as a luminescence
probe for sensing of Fe3+.

Fig. 7 Interference of different amino acid in a solution with

aspartic acid

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Fig. 8 (a) Luminescence spectra and (b) intensities of the 5D4 → 7F5 transition for 5 dispersed in different metal ions (1×10-3 mol/L)

Table 2. A summary of the MOFs for the sensing of Fe 3+ ion.

MOFs and related materials Analyte Ksv (M-1 ) Detection Ref

Limit (mol/L)
CTGU-1 (Tb) Fe3+ 1.883×106 1 × 10-9 32
[Zr6O4(OH)4(2,7-CDC)6]·19H2O·2DMF Fe3+ 5.5×103 1.80×10-8 33
Al-MIL-53-N3 Fe3+ 6.13×103 3×10-8 34
ZSB-1 Fe3+ - 5.4×10−8 35
Eu3+@MIL-124 Fe3+ 3.874×104 2.8×10-7 36
Cd2(OBA)2(BPTP)(H2O) Fe3+ - 3.6×10−7 37
NTU-9-NS(Ti) Fe3+ - 4.5×10-7 38
[Cd2(L)(bimid)(DMF)2]·(DMF) Fe3+ 3.75×104 3.70×10−7 39
[[Tb(μ6-H2cpboda)( μ2-OH2)2]·H2O]n Fe3+ 6.50× 104 8.40 ×10-7 This work
Eu−BPDA Fe3+ 1.25×104 9×10-7 40
Eu2(OH-BDC)3 Fe3+ - 1.17×10-6 41
[Zn(L)(bpe)]∙DMF Fe3+ 2.27×104 1.55×10−6 42
[Zn2(TPOM)(NDC)2]·3.5H2O Fe3+ 1.9×104 2.0×10-6 43
BUT-14 Fe3+ 2.17×103 3.8×10−6 44
[Zn2(cptpy)(btc)(H2O)]n Fe3+ 5.456×103 4.33×10−6 45
{[Cd(L)(1,4-PDA)]·0.7(C2H5OH)}n Fe3+ 1.177×104 8.51×10−6 46
[Tb(BTB)(DMF)]·1.5DMF·2.5H2O Fe3+ - 1×10−5 47
Cd2(bptc)(2,2-bipy)2(H2O)2 Fe3+ 1.9×104 1.02×10−5 48
{[Cd2(bptc)(2,2-bipy)2(H2O)2]}n Fe3+ 8.61×103 1.02×10−5 49
{[Cd(L)0.5(1,8-NDC)·H2O]}n Fe3+ 1.062×103 1.02×10−5 46
{[Cd2(bptc)(4,4-bipy)(H2O)2]·4H2O}n Fe3+ 6.21×103 2.03×10−5 49
{[Cd2(bptc)(phen)2]·4H2O}n Fe3+ 3.07×103 2.17×10−5 49
FJI-C8 (Zn) Fe3+ 8245 2.33×10−5 50
[Cd(Hcbic)]n Fe3+ 1.8×105 3.1×10-5 51
[Eu(atpt)1.5(phen)(H2O)]n Fe3+ 7.60×103 4.5×10-5 52
[Zn5(hfipbb)4(trz)2(H2O)2] Fe3+ 4.1×105 1.8×10-4 53
[Ln(µ3-cpta)(phen)(H2O)2]n Fe3+ 2138 2.0×10-4 54
HPU-1 (Zn) Fe3+ 1.0 × 104 1.09 × 10-3 55
[[Tb2(pyznpy)6·4H2O]·2H2O]n Fe3+ 7.99×104 1.5×10−3 56
H3O[In3(dcpy)4(OH)2]·3DMF·4H2O Fe3+ 4.3×103 - 57
[TbL(H2O)2]·H2O Fe3+ 1.9×103 - 58

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The influence of Fe3+ concentration on the emission quenching probing Fe3+ ion is 8.40 ×10-7 M, and the sensing ability of the
of complex 5 was evaluated (Fig. 9). The Fe3+ concentration is linear complex 5 is comparable to those of previously reported MOFs for

Dalton Transactions Accepted Manuscript

with quenching efficiency and this quenching behavior also can be
rationalized with the equation of Stern−Volmer. The quenching
constant value Ksv is 6.50 × 104 M−1 for Fe3+ and the correlation
coefficient is 0.9931. The detection limits (LOD) of the 5 system for
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sensing of Fe3+ (Table 2). Similar to detection of aspartic acid, the
influences of mixed metal cations were investigated. As shown in
Fig. 10, other metal ions have no significant effect on the
luminescence quenching caused by Fe3+ ion.

Fig. 9 (a) Luminescence responses of 5 (10.00 mg dispersed in 40.00 mL of water) toward different concentrations of Fe3+ in
water (inset: the colour change of the solution (TOP)). (b) Plot of the KSV curve between the luminescence intensity of Fe3+.

Recyclable luminescence experiments

The recycling performance is very important for a good probe.
Thus, we investigated the recycling performance of Tb-MOF as the
aspartic acid and Fe3+ luminescent probe. We dispersed complex 5
in the aqueous solution of aspartic acid and Fe3+ ion respectively
and treated them by ultrasonication for 30 min forming Tb-MOF-
aspartic or Tb-MOF-Fe3+. After washed by water several times, their
luminescence intensities were tested. As shown in Fig. 11, we found
the luminescence intensities of the Tb-MOF-aspartic/ Fe3+ ions were
nearly identical to the original one. The same behavior was
observed after five sensing–recovery cycles, which indicated that
complex 5 can be as a repeated, stable and fast probe to detect
aspartic acid and Fe3+ ion in aqueous solution.

Fig. 10 Interference of different amino acid in a solution with a

aspartic acid

Fig. 11 The luminescence intensity of complex 5 for the recognition of aspartic acid (a) , Fe3+ (b) , after five recycling processes.

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The possible mechanism of luminescence quenching
What is the possible sensing mechanism of the luminescence
quenching in response to the presence of aspartic acid and Fe 3+
cation. Firstly, the PXRD patterns of the sample were measured
after sensing of aspartic acid and Fe3+ cation, and both of them
retained the crystallinities (Fig. S9). They indicated that the
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quenching phenomenon is not caused by framework collapse. 59-60
The UV-vis spectrum of Fe3+ cation has a large overlap with the
excitation wavelength of complex 5, and the spectra of other metal
ions have no obvious overlap (Fig. S10). Thus, the competition
absorption of excitation wavelength (305nm) energy between the
complex 5 and Fe3+ aqueous solution leads to fluorescence
quenching.61-62 For aspartic acid, luminescent intensity and the
concentration of aspartic acid were able to be fitted by the
Stern−Volmer equation, which indicated that the quenching process
of complex 5 may result from a dynamic process. Meanwhile, there
is a decrease of the luminescence lifetime by the coalescence of
Fig. 12 (a) One of hydrogen-bond types between H5cpboda and DMSO; (b) UV−vis absorption spectra of suspended complex 5
(black) in H2O, and complex 5 (red) in DMSO solution.
Conclusions
In summary, we have synthesized and characterized a series of
Ln3+ metal−organic frameworks from the designed H5cpboda and
lanthanide ions. The Luminescent properties show that Tb-MOF
represents a very highly efficient quenching sensor for detecting
aspartic acid and Fe3+ ion in the aqueous solution. And the limits of
detection (LOD) are 7.95× 10−6 M for aspartic acid and 8.40 ×10-7 M
for Fe3+ ion, respectively. Moreover, the quenching effect of
aspartic acid and Fe3+ ion on Tb-MOF luminescence is not
influenced by the presence of other amino acids or metal cations. In
addition, the reproducibility experiments show that Tb-MOF has
good recyclability for sensing aspartic acid and Fe3+ ion. Most
interestingly, the fluorescence intensity of Tb-MOF is enhanced
obviously with the increment of DMSO content in aqueous solution.
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aspartic acid in composites (Fig. S11). Thus, the collision interaction
between aspartic acid and framework of complex 5 leads to the
Dalton Transactions Accepted Manuscript
energy loss, which results in luminescence quenching.63
The possible mechanism of luminescence enhancement
Finally, the consistent PXRD patterns confirm that the framework
remains stable after detecting DMSO (Fig. S12), which indicates the
luminescent enhancement doesn’t result from the framework
collapse. Sulfur elemental analysis of samples after detecting DMSO
found that there is S (0.27%). Thus, it could be the lone pair of
electrons in the O of DMSO and the proton of carboxylic acid of
H5cpboda forming a hydrogen bond (Fig. 12), which leads to the
luminescence enhancement effects.29,64 The existence of hydrogen
bonds can also be proved by UV−vis absorption spectra of
suspended complex 5 in H2O and DMSO solution respectively (Fig.
12b), in which the positions of the peaks red-shift from 300 nm to
310 nm. Therefore, the luminescence enhancement effect of
complex 5 is caused by hydrogen bonding interaction.
Moreover, the perfect linear correlation between the luminescence
intensity of Tb-MOF and the values of DMSO/H2O provides a high
selectivity and stable luminescent sensor to determine DMSO. And
the fluorescence intensity of Tb-MOF in the volume fraction of
DMSO/H2O (100%) is 18.85 times higher than that of DMSO/H2O
(0.0%). To our knowledge, this is the first time that luminescence
Ln- MOF materials have been used as a “turn on” probe for
detecting DMSO. Hence, the complex 5 can be a multi-responsive
luminescent probe to detect aspartic acid, Fe3+ ion and DMSO in
aqueous solution.
Conflicts of interest
There are no conflicts of Interest to declare.
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Journal Name ARTICLE

Acknowledgements Crystengcomm, 2018, 20, 5442-5456. View Article Online

31 G. Ji, T. Zheng, X. Gao and Z. Liu, Sens.DOI: Actuator B., 2019, 284,
10.1039/D0DT00938E
Authors gratefully acknowledge the Natural Science Foundation of 91-95.
China (Grant Nos 21671124 & 21571118) and 32 M.-L. Han, G.-W. Xu, D.-S. Li, Azofra, M. L, J. Zhao, B. Chen, C.
the Natural Science Foundation of Shanxi Province (201701D121039 Sun, ChemistrySelect . 2016, 1, 3555-3561.
33 A. Das, S Biswas, Sens. Actuators, B, 2017, 250, 121-131.
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the Scientific Instrument Center of Shanxi University of China. 47, 2690-2700.
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A first Ln−MOF as a trifunctional luminescent probe for efficient

sensing of aspartic acid, Fe3+ and DMSO

Dong-Dong Yanga, Li-Ping Lu*a, Si-Si Fengab, Miao-Li Zhu*ab

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Graphical Abstract
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A first Ln−MOF (Tb-MOF) as a trifunctional luminescent probe for efficient sensing of aspartic
acid, Fe3+ and DMSO.