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A First LN MOF As A Trifunctional Luminescent Probe For Efficient
A First LN MOF As A Trifunctional Luminescent Probe For Efficient
A First LN MOF As A Trifunctional Luminescent Probe For Efficient
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An international journal of inorganic chemistry
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Douglas W. Stephen et al.
N-Heterocyclic carbene stabilized parent sulfenyl, selenenyl,
shall the Royal Society of Chemistry be held responsible for any errors
and tellurenyl cations (XH+, X = S, Se, Te)
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ARTICLE
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.
available from commercial sources and without further purification. [[Eu(μ6-H2cpboda)(μ2-OH2)2]·1.216H2O]n (4). Yield 68% View relative to
Article Online
A Bruker TENSOR27 spectrometer to measure FT-IR and it was Eu. Anal. Calcd. (C23H17.52EuO15.26): C 40.03, DOI: 10.1039/D0DT00938E
H 2.54. Found: C 40.01,
recorded from KBr pellets in the range of 4000–400 cm−1. H 2.56. IR (KBr, cm−1): 3440(m), 1678(m), 1547(s), 1383(s), 1282(m),
Thermogravimetric data (TGA) were gotten using Dupont thermal 1131(m), 1014(m), 905(w), 770(m), 707(w), 603(w).
analyzer in range of RT–800 °C under nitrogen flow with a heating
[[Tb(μ6-H2cpboda)(μ2-OH2)2]·H2O]n (5). Yield 68% relative to Tb.
rate of 10 °C min−1. Powder X-ray diffraction (PXRD) data were
Anal. Calcd. (TbC23H17O15): C 39.87, H 2.46. Found: C 39.78, H 2.51.
recorded on a Bruker D8 Advance X-ray diffractometer with Cu Kα
IR (KBr, cm−1): 3446m, 1672m, 1622m, 1552s, 1389s, 1137m,
radiation (λ = 1.5418 Å) and the data were recorded within the 2
1024m, 905w, 773w, 604w.
range of 5–50°. Elemental analyses of compounds were performed
using a Perkin-Elmer 240 elemental analyzer. The fluorescence X-ray crystallography
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
ARTICLE
As shown in Fig. 1a, the asymmetric unit of complex 5 contains by H2cpboda3- ligands coordinated to Tb(III) ions to give rise to a 3D
one unique Tb(III) atom, one partial protonation ligand coordination framework (Fig. 1d).
(H2cpboda3-), two coordinated H2O molecules and one free H2O To gain a better insight into the nature of the 3D Ln-MOF
molecule. Each Tb3+ ion is eight-coordinated by oxygen atoms structure, the topological method TOPOS program28 was employed.
exhibiting a distorted {TbO8} geometry (Fig. 1b), and oxygen atoms As shown in Fig. 1e, each H2cpboda3- ligand acts as a 6-connected
are derived from six H2cpboda3- ligands (O1, O2i, O6ii, O7iv, O9v, node and each Tb(III) ion also act as 6-connected node. Thus, the
O11iii), and two H2O molecules (O13, O14). The Tb–O bond lengths structure can be simplified as a 6,6-connected net, which is a new
and O—Tb—O bond angles are in the ranges of 2.302(4) to 2.468(5) topological net with point symbols (413·62)(48·66·8) (Fig. 1e).
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 PXRD patterns and thermal analysis
H2cpboda3- ligand links six Tb(III) ions with a μ5-η1:η1:η1:η1:η1:η1 PXRD patterns of complexes 1−5 are also carried out room
coordination mode, and the four carboxylates of the H2cpboda3- temperature to check the purity. As shown in Fig. S2, most peak
ligand adopt two different coordination modes (η1:η0, η1:η1), with positions in simulated and experimental patterns are consistent,
the distance of adjacent Tb3+ ions of 5.4829(3) and 5.5394(4) Å, demonstrating the phase purity of the bulk sample. The thermal
respectively. The Tb(III) ions are connected by carboxylates to form stabilities of complexes 1–5 were characterized by TGAs from RT to
a 1D chain, and the 1D chains are bridged by H2cpboda3- ligands to 800 °C at the heating rate of 10 °C min−1 under a N2 atmosphere
form a 2D layer structure (Fig. 1c). The adjacent layers are jacked up
(Fig. S3) and their thermal decomposition curves are also similar. Thus, View Article Online
DOI: 10.1039/D0DT00938E
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 don’t show characteristic emission bands, which indicates that the
stability (Fig. S3). The weight loss of complex 1 in the range of 65– energy absorbed by the ligand cannot be transferred to the excited
250°C is a total loss of 8.91%, which corresponds to the release of state of the Ln(III) ion.
two coordinated H2O molecules and the solvent H2O molecule The emission spectrum of complex 4 (Figure. 2b) showed four
(calcd 8.96%). And the network of this compound presents a typical Eu3+ emissions. The one at 593 nm is distributed to magnetic
plateau until approximately 400°C. Then the framework undergoes dipolar 5D0 → 7F1, more intense than that of the emission at 613 nm
decomposition in the range of 400–800 °C. which is from the electric dipolar 5D0 → 7F2 transition. The two
Photoluminescent properties. emission peaks at 650 and 698 nm are assigned to the 5D0 →7F3 and
5D → 7F transitions, respectively.
0 4
As shown in Fig. S4, under the irradiation of ultraviolet light,
complexes 4 and 5 shows intense visible red and green fluorescence, For 5, it exhibits characteristic Tb3+ peaks at 489, 543, 587and
respectively. The solid-state luminescence spectra of complexes 1-5 620 nm, corresponding to the 5D4 → 7Fj (j = 6, 5, 4, 3) transitions,
and H5cpboda were measured at ambient temperature. For 1, the respectively (Fig. 2c). Among the emission lines, the strongest
emission spectrum shows a weak band at 412 nm under the intensity of emission at 543 nm is attributed to the 5D4 → 7F5
excitation at 325 nm (Fig. 2a), which may be due to the emission of transition.
ligand-to-metal charge transfer (LMCT). The complexes 2 and 3
4 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx
ARTICLE
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. prompt us to evaluate the suitability of 5 for sensing applications. In
We studied the fluorescence properties of complexes 1, 4 and 5 complex 5. Furthermore, to explore the solvent and pH stability of
in these common organic solvents. The samples of complex 1, 4 and the complex 5, then soak the sample of complex 5 in different
5 (2.0 mg) were dispersed in 5.0 mL of different organic solvents organic solvents and pH for 24 hours, and then the samples were
(dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), N,N- recollected by centrifugation and air-drying before PXRD
dimethylformamide (DMF), methanol, ethanol, dichloromethane, measurement. The patterns conform with the theoretical ones,
acetonitrile, acetone and aqueous solution), then treated by which suggests 5 has good solvent stability (Fig. S7and S8). The
ultrasonication for 30 min before the luminescence measurements. various organic solvents display different effects on the emission of
As shown in Figures 3, S5 and S6, the complex 1 and 4 displays a Tb-MOF, and the Tb-MOF exhibited the weakest emission in
weak luminescence in common organic solvents and no fixed peak acetone. It is worth noting the Tb-MOF exhibits a much higher
shape. Compared with complex 1 and 4, 5 has stronger emission emission band in DMSO than that in other solvents.
intensity in organic solvents and excellent solvent stability of 5
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.
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- (Try), L-isoleucine (Iso), L-histidine (His), L-valine (Val), L-proline
MOF, it is very necessary to do the detection of different content (Pro), L-glutamic acid (Glu) and L-aspartic acid (Asp)) to study its
DMSO in aqueous solution. As shown in Fig. 4a, we found that the selectivity and detection of amino acids at room temperature. As
fluorescence intensity of Tb-MOF enhanced obviously with the illustrated in Fig. 5, compared to other amino acids, glutamic acid
increment of DMSO content in aqueous solution. The colour of the showed less pronounced quenching and the aspartic acid has
system varies from green to yellow-green. In addition, we can see obvious annihilation on the fluorescence intensity of Tb-MOF. Thus,
that when the volume fraction of DMSO increases to close to 100%, the Tb-MOF can also be seen as a promising luminescence probe for
the fluorescence intensity is the strongest and the fluorescence sensing of aspartic acid among amino acid.
intensity of the DMSO/H2O (100%) is higher 18.85 times than that In order to understand the sensitivity of 5 as a luminescent
of DMSO/H2O (0.0%). Moreover, the values of DMSO/H2O exhibit a sensor of aspartic acid, the relationship between the concentration
good linear relationship with DMSO in the volume fraction. The of the aspartic acid and the luminescence intensities of the Tb-MOF
linearity can be fitted as a function as follow:29 was studied. A 5 mg of complex 5 was dispersed in 10 mL of distilled
I/I0 = 0.1970VDMSO/H2O -0.4410 (1) water forming uniform suspension, and then aspartic acid (1.0 × 10-
3 M) was gradually added to the suspensions. As shown in Fig. 6,
The I0 is the initial luminescence intensity, and I is the
luminescence intensity after the addition of the DMSO content. The with an increasing of aspartic acid, the luminescent intensities
calculated values of the correlation coefficient (R2) is 0.9914, and gradually decreased. This luminescence quenching can be
the limit of detection (LOD) for DMSO is calculated as 1.68% based calculated by the Stern–Volmer equation: I0/I = 1+ Ksv [M]30-31 (I0 is
on eq (2): the emission intensity of Tb-MOF prior; I is the emission intensity
after adding the aspartic acid; [M] is the concentration of the
3S B
LOD analytes). The Stern–Volmer plots for aspartic acid are almost linear
S (2) at low concentrations, with a correlation coefficient of 0.9956. The
Ksv value of 9.80×103 M−1 indicates the remarkable influence of
The SB is standard deviation from five blank measurements for
aspartic acid on quenching the emission of 5 (Fig. 6b). By a ratio of
H2O solution, and the S is the slope of the linear relationship in the
LOD = 3σ /m we calculated the limit of detection (LOD) for aspartic
inset of Fig. 4b. The result indicates that complex 5 could be a good
acid, where σ for standard deviation for Tb-MOF calculated from
fluorescent probe to detect DMSO in aqueous solution.
five blank measurements and m for slope of the linear curve for
plotted Tb-MOF at lower concentration. The detection limit of the
Sensing of amino acid Tb-MOF system for probing aspartic acid was 7.95×10−6 M. The
Secondly, considering good luminescent properties of complex 5, sensing ability of the Tb-MOF systems is comparable to those of
we have found that the Tb-MOF can also be used for detection previously reported MOFs for detection of aspartic acid (Table S1).
amino acids in water. A 10 mg of the complex 5 is dispersed in 40 Further, we investigated the influence on the system of mixed
mL distilled water and treated by ultrasonication for 30 min to form amino acids. As shown in Fig. 7, there is no significant effect of
uniform suspension. Then the suspensions were respectively added other amino acids on the luminescence quenching caused by
100 of µL (1.0 × 10-3 M) aqueous solution included different amino aspartic acid.
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 This journal is © The Royal Society of Chemistry 20xx
ARTICLE
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+.
ARTICLE
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)
ARTICLE
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
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+.
Fig. 11 The luminescence intensity of complex 5 for the recognition of aspartic acid (a) , Fe3+ (b) , after five recycling processes.
ARTICLE
The possible mechanism of luminescence quenching aspartic acid in composites (Fig. S11). Thus, the collision interaction
What is the possible sensing mechanism of the luminescence between aspartic acid and framework of complex 5 leads to the
quenching phenomenon is not caused by framework collapse. 59-60 luminescent enhancement doesn’t result from the framework
The UV-vis spectrum of Fe3+ cation has a large overlap with the collapse. Sulfur elemental analysis of samples after detecting DMSO
excitation wavelength of complex 5, and the spectra of other metal found that there is S (0.27%). Thus, it could be the lone pair of
ions have no obvious overlap (Fig. S10). Thus, the competition electrons in the O of DMSO and the proton of carboxylic acid of
absorption of excitation wavelength (305nm) energy between the H5cpboda forming a hydrogen bond (Fig. 12), which leads to the
complex 5 and Fe3+ aqueous solution leads to fluorescence luminescence enhancement effects.29,64 The existence of hydrogen
quenching.61-62 For aspartic acid, luminescent intensity and the bonds can also be proved by UV−vis absorption spectra of
concentration of aspartic acid were able to be fitted by the suspended complex 5 in H2O and DMSO solution respectively (Fig.
Stern−Volmer equation, which indicated that the quenching process 12b), in which the positions of the peaks red-shift from 300 nm to
of complex 5 may result from a dynamic process. Meanwhile, there 310 nm. Therefore, the luminescence enhancement effect of
is a decrease of the luminescence lifetime by the coalescence of complex 5 is caused by hydrogen bonding interaction.
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.
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This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 11
A first Ln−MOF (Tb-MOF) as a trifunctional luminescent probe for efficient sensing of aspartic
acid, Fe3+ and DMSO.