Ratiometric fluorescence detection of trace water in an organic solvent based on bimetallic lanthanide metal-organic frameworks

Article abstract of DOI:10.1039/c9cc02324k

Here we report a new sensor Tb_97.11Eu_2.89-L1 that enables ratiometric detection of trace water in CH₃CN. As the water content increases from 0% to 2.5% (v/v%), Tb_97.11Eu_2.89-L1 exhibits an excellent l

Full text of DOI:10.1039/c9cc02324k

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C9CC02324K
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Ratiometric fluorescent detecting trace water in organic solvent
based on bimetallic lanthanide metal-organic frameworks
Beibei Li,ac Wenjing Wang,*ac Zixiao Hong,b El-Sayed M. El-Sayedacd and Daqiang Yuan*ac
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Here we report a new sensor Tb97.11Eu2.89-L1 that achieves self-built-in corrections of two signal peaks and thus affords
ratiometric detection of trace water in CH3CN. As the water content more accurate measurement. On the other hand, recent
increases from 0% to 2.5% (v/v%), Tb97.11Eu2.89-L1 exhibits an researches have indicated that lanthanide-based metal-organic
excellent linear relationship between water content and I543/I615, as frameworks (Ln-MOFs) are promising ratiometric sensor
well as variable emissive light colors visible to the naked eye.
materials because of their high color purity, nonoverlapping
spectra, narrow emission characteristic bands, and large Stokes
shifts. In recent years, a series of ratiometric sensor materials
based on MOFs have been successfully prepared.11 Although
some significant advances have been made in ratiometric
probes, it has still been a very challenge task to obtain probes
with highly specific selectivity for a target product to date.
Detection and quantification of low amounts of water in
gases or organic solvents is of exceptional importance in
industrial processes and environmental monitoring.12
Frequently, Karl Fischer titration and electrochemical methods
are used for the determination of water;13 however, these
methods are limited in practical applications due to the
necessity for specialized instruments and complicated
operation. Therefore, water sensing based on fluorescent MOFs
has attracted extraordinary attention attributable to their
various advantages, including fast response time, low detection
limit, simple operation, and even naked eye detection.14 Recent
studies have shown that ESIP-type fluorescent sensors based on
MOFs are suitable for detection and quantification of trace
amount of water.15 In addition, some ratiometric sensors based
on Ln-MOFs also offer worthy performance for trace water
detection.16 Although some achievements have been made in
design and synthesis of water probes, the probes with high
selectivity and sensitivity are still rare so far. In this work, we
adopt the mixed-lanthanide strategy that achieves sensitive
ratiometric fluorescence detection of low-level water in
acetonitrile (CH3CN).
Metal-organic frameworks (MOFs), also known as porous
coordination polymers, are constructed from organic linkers
and metal ions to form highly ordered structure with chemically
adjustable porosities and high surface area.1 Emerging as an
intriguing class of porous crystalline materials, MOFs have
received tremendous attention due to their extensive scope of
applications including gas storage and separation,2 drug
delivery,3 catalysis,4 and magnetism5 over the past two decades.
Apart from these applications, MOFs have emerged as
functional luminescent materials for chemical sensing, because
the self-assembly of metal ions or clusters and organic
luminescent moieties into porous MOFs can render luminescent
platforms.6 Furthermore, some guest molecules within MOFs
can also induce luminescence.7 The sensing capability of MOFs
is determined by interaction of its framework with various
analytes, just like gases,8 volatile organic compounds,9 and
metal cations/anions10. Although “turn-on” probes can
efficiently improve the sensitivity compared with “turn-off”
probes, a significant limitation is that the fluorescent accuracy
is strongly influenced by the environmental factors when using
the sole sensing signal for the target analyte. However, this
problem can be overcome by a ratiometric sensor, which has
a. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China.
b. Institute of Urban Environment, Chinese Academy of Sciences, Xiamen, 361021,
China
The reaction of Tb(NO3)3·6H2O or Eu(NO3)3·6H2O, hexakis-(4-
carboxylatophenoxy)cyclotriphosphazene (H6L1) and acetic
acid under hydrothermal condition resulted in colorless crystals
of compound Tb-L1 or Eu-L1, respectively. Single-crystal X-ray
diffraction analyses reveal that compounds Tb-L1 and Eu-L1 are
isomorphic (Table S1, Fig. S1, S2). Different from the previously
c. University of the Chinese Academy of Sciences, Beijing, 100049, China.
d. Chemical Refining Laboratory, Refining Department, Egyptian Petroleum
Research Institute, Nasr City, Cairo, 11727, Egypt
† E-mail: wjwang@fjirsm.ac.cn; ydq@fjirsm.ac.cn
Electronic Supplementary Information (ESI) available: Experimental details,
supporting figures and graphs, and crystallographic data tables. CCDC 1902862 and
1902863. For ESI and crystallographic data in CIF or other electronic format see
DOI: 10.1039/x0xx00000x
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reported structure, compound Tb-L1 here crystallizes in the excited state of lanthanides to the O-H oscillatorsVoiefwthAreticbleoOunlninde
monoclinic system with the space group C2/c.17 The asymmetric water molecules and results in a rise of the luminescent
DOI: 10.1039/C9CC02324K
unit of Tb-L1 consists of 2.5 crystallographically independent intensity.16c, 19 Meanwhile, the luminescence intensity of ligand
Tb3+ ions, one deprotonated ligand, 1.5 terminal water remains almost unchanged. When gradually increasing the
molecules, and 1.5 bridged OH groups. As shown in Fig. 1, Tb-L1 water content in CH3CN, the characteristic emission intensities
displays three-dimensional (3D) rod-packing structures in which of the Eu3+ and Tb3+ are declined accordingly. In contrast, the
each Tb3+-carboxylate infinite SBU is connected to other four ligand fluorescence intensity is correspondingly enhanced. It is
chains through the cyclotriphosphazene portion of the H6L1. worth noting that the coordination number of lanthanide ions
Accordingly, the Tb3+/Eu3+ mixed-lanthanide Tb97.11Eu2.89-L1 can here is eight, so we speculate that the excess water molecules
be easily synthesized by varying the original molar ratios of will further coordinate with the lanthanide ions. The more O-H
Tb(NO3)3·6H2O to Eu(NO3)3·6H2O via the above-mentioned oscillators of the bound water molecules maybe reduce the
method. As expected, the structure of Tb97.11Eu2.89-L1 is energy transfer efficiency from the ligands to lanthanide ions.
isostructural to Tb-L1 and Eu-L1, as confirmed by powder X-ray As a result, the fluorescence intensity of the ligand elevates, and
diffraction (PXRD) (Fig. S3). The UV absorption spectra of solid the fluorescence intensity of the lanthanide ions decrements.
Tb-L1 and Eu-L1 were recorded (Fig. S4, S5). The contents of As the water content raises from 0% to 2.5% (v/v%), the
Tb3+ and Eu3+ ions in Tb97.11Eu2.89-L1 were confirmed by characteristic luminescence shows an intensity reduction of
inductively coupled plasma spectroscopy (ICPs). Elemental 37% for the 5D0→7F2 of Eu3+ and 33% for the 5D4→7F5 of Tb3+ (Fig.
mapping analysis shows that the Tb3+ and Eu3+ are evenly 2c, d). Different fluorescence quenching abilities for Tb3+ and
distributed in one crystal (Fig. S6). Zeo++ calculations indicate Eu3+ can be ascribed to their differences in energy gap (12000
that the void space in Tb97.11Eu2.89-L1 is about 65.4% of the total cm-1 for Eu3+ and 15000 cm-1 for Tb3+).20 Besides, the linear
crystal volume.18
relationship between the emission intensities and the water
content is not good for Tb-L1 and Eu-L1 (Fig. S7, S8). Therefore,
Tb-L1 and Eu-L1 are not suitable to quantitatively measure
water content in CH3CN.
Fig.1 Crystal structure of Tb-L1 indicating (a) 1D Tb3+-carboxylate chain as the
infinite SBU and (b) the crystal packing viewed along the crystallographic direction
(Tb, green polyhedra; C, black; O, red; N, blue; P, pink; H atoms are omitted for
clarity).
For detecting water content in organic solvents, the Tb-L1
and Eu-L1 were ground and dispersed in dry CH3CN at room
temperature. With the excitation at 280 nm, Tb-L1 exhibits very
strong characteristic transitions (5D4→7FJ, J = 6-3) of Tb3+ at 488,
543, 583 and 620 nm, while Eu-L1 shows the characteristic
transitions (5D0→7FJ, J = 1-4) of Eu3+ at 591, 615, 651 and 698
nm (Fig. 2a, b). The luminescent behaviors of Tb-L1 and Eu-L1
indicate that ligand H6L1 is a good sensitizer for the Tb3+ and
Eu3+ based on the antenna effect. The luminescent quantum
yields are 20.25% for Tb-L1 and 9.24% for Eu-L1, respectively.
However, the emission intensity of Tb3+ is much higher than that
of Eu3+. Besides, the emission intensity of H6L1 located at 403
nm in Eu-L1 is more obvious than that of Tb-L1. This result
clearly suggests that intramolecular energy transfer from the
ligand H6L1 to Tb3+ is much more effective than that to Eu3+. At
the beginning of adding water into CH3CN solution, the
luminescent intensities of Tb-L1 and Eu-L1 are incremented.
This unusual phenomenon may be caused by the formation of
hydrogen bonds between water and the coordinated water
molecules, which can lower the energy transfer from the
Fig.2 (a) Emission spectrum of Tb-L1 in CH3CN. (b) Emission spectrum of Eu-L1 in
CH3CN. Inset: the corresponding optical images irradiated under a 254 nm UV
lamp. (c) The fluorescence spectra of Tb-L1 for different amounts of water. (d) The
fluorescence spectra of Eu-L1 for different amounts of water.
For ratiometric sensing applications, the representative
mixed lanthanide Tb97.11Eu2.89-L1 was then used to measure
water content quantitatively. From the optical photos
illuminated by ultraviolet light (254 nm), we can observe that
Tb97.11Eu2.89-L1 displays variable colors at different water
contents in CH3CN with the naked eye. As the water content
increases from 0% to 17.6%, the color of Tb97.11Eu2.89-L1
changes from red-orange, yellow to green (Fig. 3a). With the
excitation at 280 nm, the compound Tb97.11Eu2.89-L1 shows
characteristic transitions of both the Tb3+ and Eu3+ ions in dry
CH3CN. Similar to the fluorescence behavior of Tb-L1 and Eu-L1,
the emission intensity of Tb97.11Eu2.89-L1 is enhanced upon
contacting water in CH3CN.
2 | J. Name., 2012, 00, 1-3
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However, the linear relationship between ITb/IEu and water
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content is not good for CH3OH, DMF aDnOdI:D10M.1S0O39./CIt9CisC0w2o32r4thK
noting here that acetone exhibits dramatic fluorescence
quenching of Tb97.11Eu2.89-L1 (Fig. S20, S21). The reason is that
as previously reported, acetone molecules weaken the energy
transfer from H6L1 to the lanthanides due to the absorption
band overlap between acetone and ligand H6L1.21 Therefore,
Tb97.11Eu2.89-L1 exhibits good selectivity for water over different
organic solvents, and shows quantitative detection of trace
water in CH3CN.
To visually demonstrate the color change of Tb97.11Eu2.89-L1
accompanying water absorb/release processes, we simply
deposited small amounts of the as-synthesized Tb97.11Eu2.89-L1
onto glass slides. The solid crystals Tb97.11Eu2.89-L1 contain DMA
solvent molecules in pores, which change the color slowly from
red-orange to green in air when viewed under a 254 nm UV
lamp irradiation. When using argon blowing or heating at 80 °C
for a few minutes, the color of Tb97.11Eu2.89-L1 will restore
immediately. These results clearly indicate that Tb97.11Eu2.89-L1
can absorb and release water molecules from/into air
atmosphere. More interestingly, the activated solid crystals
Tb97.11Eu2.89-L1, which exchanged with dry acetonitrile,
exhibited different response capability to water compared with
the as-synthesized sample. When the activated crystals were
placed onto glass slides in air, we can observe that the color of
Tb97.11Eu2.89-L1 gradually changed immediately from orange-
red, yellow to green in two minutes under ultraviolet light (254
nm). The reason for this quick discoloration here is because
acetonitrile molecules in the pores volatilize much faster than
DMA molecules. As the acetonitrile molecules evaporate, water
molecules gradually enter the pores and contact with metal
sites and eventually leading to a quick change in color.
Therefore, this sensor of Tb97.11Eu2.89-L1 is suitable for the
application as a novel sensitive water detector based on its fast-
responding to water. Also，no significant fluorescence changes
were observed after five dry-wet cycles in dry Tb97.11Eu2.89-L1,
confirming the good reversibility of this sensor (Fig. S22).
Fig.3 (a) Optical images of Tb97.11Eu2.89-L1 under a 254 nm UV lamp after treatment
with various amounts of water in CH3CN. (b) The fluorescence spectra of
Tb97.11Eu2.89-L1 for different amounts of water. (c) CIE chromaticity coordinates of
Tb97.11Eu2.89-L1 after treatment with various amounts of water under the
excitation wavelength of 280 nm.
Further increasing water content in CH3CN leads to the
decrement of the emission intensity for Tb3+ and Eu3+ and
increment for the ligand. As the water content ascends from 0%
to 2.5% (v/v%), the characteristic luminescence shows an
intensity reduction of 75% for the 5D0→7F2 of Eu3+, 18% for the
5D4→7F5 of Tb3+ and increment of 345% for the ligand (Fig. 3b).
Besides, due to the hydrophilic cavity of Tb97.11Eu2.89-L1, the
color changes rapidly in a few seconds upon contact with water.
The emission spectra of Tb97.11Eu2.89-L1 for different water
content (0-2.5%) in CH3CN exhibit a chromaticity shift from
orange, yellow to white according to the change in the intensity
ratio between ligand, Tb3+ and Eu3+ peaks. Additionally, based
on the 1931 Commission Internationale d’Eclairage (CIE)
chromaticity diagram, the corresponding chromaticity
coordinate change from (0.500, 0.413) to (0.330, 0.348) (Fig.
3c). It is interesting that Tb97.11Eu2.89-L1 exhibits white light
emission when the water content reaches 2.5%; however, it is
still very rare in MOFs system to achieve white light emission by
adjusting the water content in an organic solvent. As the
quenching efficiency of water to Eu3+ is higher than Tb3+, and
eventually causes the solution color to change from white to
green. Importantly, Tb97.11Eu2.89-L1 shows an excellent linear
relationship between emission ratios (I543/I615) and water
content from 0% to 2.5%, indicating that Tb97.11Eu2.89-L1 is
potentially useful for quantitative determination of trace water
in an organic solvent. As the water content increases, the
fluorescence intensity of Eu3+ quenches more significantly than
Tb3+, which eventually leads to an increase in I543 /I615. The linear
regression equation of ratiometric fluorescence and water
content change from 0% to 2.5% can be seen as y=0.46x+0.55
and the correlation coefficients R2 reach up to 0.999 (Fig. 4a).
The detection limit is as low as 0.04% (Fig. S9). However, the
linear relationship begins to deteriorate as the water content
continues to increase (Fig. S10). Therefore, this sensor of
Tb97.11Eu2.89-L1 is suitable for detecting low concentration of
water in an organic solvent. In addition, Tb97.11Eu2.89-L1 also
exhibits good selectivity for water over different organic
solvents, such as methanol (CH3OH), N,N’-dimethylformamide
(DMF) and dimethylsulfoxide (DMSO). With the variation of
water content in diverse solvents, the luminescence colors and
ratios of ITb/IEu show significant differences (Fig. S11-S19).
Fig.4 (a) The linear relationship between the fluorescence intensity I543/I615 and
the water content. (b) Optical images showing fluorescence switch of the as-
synthesized Tb97.11Eu2.89-L1 on heating or Ar blowing and then cooling in air. (c)
Optical images showing fluorescence changes of the CH3CN-exchanged
Tb97.11Eu2.89-L1 in air. All the solids are dispersed on the glass slides with 254 nm
UV lamp irradiation.
In summary, we report a new sensor Tb97.11Eu2.89-L1 that
achieves ratiometric detection of trace water in CH3CN.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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48, 500-503; (e) M. Wang, L. Guo and D. Cao, Sens. Actuators, B,
Tb97.11Eu2.89-L1 displays variable colors at different water
content in CH3CN with the naked eye illuminated by ultraviolet
light. As the water content grows from 0% to 2.5% (v/v%),
Tb97.11Eu2.89-L1 exhibits an excellent linear relationship between
water content and I543/I615. The detection limit is as low as 0.04%.
Besides, Tb97.11Eu2.89-L1 shows a reversible fluorescence color
change after absorbing/releasing water molecules. Therefore,
Tb97.11Eu2.89-L1 represents an excellent water-sensing material
for detecting trace water in an organic solvent.
This work was supported by the Strategic Priority Research
Program of the Chinese Academy of Sciences (XDB20000000),
the Key Research Program of Frontier Sciences, Chinese
Academy of Sciences (QYZDB-SSW-SLH019), and the National
Natural Science Foundation of China (21707143).
2018, 256, 839-845; (f) B. Chen, L. Wang, F. ZapatVai,ewGA. rQticilaenOnalninde
DOI: 10.1039/C9CC02324K
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ChemComm
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Journal Name
COMMUNICATION
Table of Content
View Article Online
DOI: 10.1039/C9CC02324K
A highly sensitive sensor Tb97.11Eu2.89-L1, which represents an
excellent water-sensing material for detecting trace water in an
organic solvent, is reported.
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