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Journal of Materials Chemistry C Accepted Manuscript

ARTICLE

Functional Microscale Single-phase White Emission Lanthanide

MOF for Tunable Fluorescent Sensing and Water Quality
Published on 20 February 2019. Downloaded by Washington University in St. Louis on 2/20/2019 3:50:24 PM.

Received 00th January 20xx,

Monitoring
Accepted 00th January 20xx
Tiancheng Sun, Ping Wang, Ruiqing Fan,* Wei Chen, Sue Hao and Yulin Yang*
DOI: 10.1039/x0xx00000x
Developing novel fluorescent material to rapidly and reliably differentiate organic molecules and polluting ions in water
www.rsc.org/
quality monitoring is highly challenging. Here, by taking advantage of facile preparation and sensitive recognition ability, a
fluorescent platform based on novel microscale heterometallic lanthanide metal-organic framework Eu0.059Tb0.051Gd0.89-
DPON (H3DPON=5-(3,4-dicarboxylphenoxy) nicotic acid) is constructed for effective combination of molecules/ions
recognition and logic computing. The tri‐emission lanthanide metal-organic framework (Ln-MOF) exhibits notable fingerprint
correlation between various solvent molecules/cations and the emission intensity ratio of ligand, Tb3+ and Eu3+. Furthermore,
Ln-MOF shows fast and sensitive recognition of formol both in aqueous solution and vapor. Similarly, an efficient turn-on
ratiometric fluorescent probe for VO43- is designed, which is the first use of Ln-MOFs as fluorescent sensors for VO43-.
Moreover, Eu0.059Tb0.051Gd0.89-DPON realizes multi-component analysis (Fe3+, VO43-, and S2−) in water through the
construction of Boolean logic system, also obtains a password lock security system by sequential logic operation. The
comined merits of outstanding specific surface area and strong molecular/ionic recognition make Eu0.059Tb0.051Gd0.89-DPON
a promising material for applications in the fields of intelligent multi-components analysis and water quality monitoring.

materials for fast and accurate recognition and distinction of

Introduction various molecules or ions in aqueous solution have not been
well investigated.
Water monitoring is a major concern in the world because of
In recent years, information technology has advanced
the increasing toxic substances emissions such as organic
significantly and brings huge influence on the molecular
molecules, metal ions and anions, which is extremely relevant
chemical field.22,23 Considering the powerful molecular
for food safety, human health and environmental safety. 1-3 As
information processing capabilities, molecular computer can
we all know, most of organic molecules are the culprit of
provide a viable way to break the limit of the conventional
deformity, mutation and cancer, and they could be
electronic computer and to develop artificial intelligence.
concentrated through the food chain.4-7 Among them, formol is
Therefore, molecular logics that combine chemical inputs with
a toxic molecule, which is famous as culprit of leukemia. 8,9 As
measurable fluorescence outputs have captured increasing
for most metals ions and anions, because of the features of
attention. Nowadays, the reported fluorescent logic gates
toxic, stabilization, concealment and accumulation, the impact
mainly rely on various DNA molecules, while some intrinsic
of these ions on environment, biology and human is serious and
drawbacks of DNA molecules increase inconvenience in
lasting.10-12 It is well known that Vanadium is an essential trace
practical application. Advanced logic circuits at the molecular
element for human body, but once the content is excessive, it
level are rarely achieved due to the complex process as well as
will become toxic and accumulate in vivo, especially V 5+ in VO43-
single and unstable output. Also, the uncertain DNA
.13,14 Therefore, the recognition and detection of different
amplification efficiency results in a low accuracy input
organic molecules and ions has received great attention. Among
signal.22,24 Therefore, a fluorescence material with ability of
various analytical methods, fluorescent sensors exhibit many
recognizing one or more certain analytes in one system is
advantages in detection, such as good reliability, high sensitivity
needed for the construction of advanced logic gates.
and real-time detection.15-17 Although some fluorescent metal-
As a promising class of luminescence materials, Ln-MOFs
organic frameworks (MOFs) materials show strong recognition
have gathered extensive attention for its application in chemical
ability on various molecule or ion,18-21 fluorescent MOFs
recognition owing to the combination of intrinsic porosity of
MOFs and inherent luminescence features of lanthanide
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion elements.25-28 The host–guest interactions (coordination bonds,
and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of
Technology, Harbin 150001, P. R. China
π–π interactions, or hydrogen bonding) endue Ln-MOFs with
*E-mail: [email protected] and [email protected]. high sensing sensitivity for some molecules, metal ions, and
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x

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information processing performance. This logic circuit will Online

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DOI: 10.1039/C8TC05968C
to realize multiple analyte inputs for multicomponent analysis
and it will become an opportune candidate for water
environment monitor.

Journal of Materials Chemistry C Accepted Manuscript

Scheme 1. The synthesis process of Eu0.059Tb0.051Gd0.89-DPON and its application Results and discussion
on multicomponents analysis in water.
Description of the crystal structures
anions.29-33 It is well known that the change of single emission Single-crystal X-ray diffraction analysis reveals that all
intensities of Ln-MOFs depends on many uncontrollable factors, {[Ln(DPON)(H2O)2]·(H2O)}n compounds are isomorphous, and
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_
such as the preparation method of probes, concentration and crystallize in triclinic system P1 space group. The structure of 3-
instrument parameters.34-36 Therefore, the sensing of small Eu is introduced in detail as a representative (Fig. 1). The
molecules/ions through ratios of relative emission intensities in crystallographically independent Eu3+ ion in the asymmetric
multi-fluorescent centers Ln-MOFs is more reliable and structural unit is coordinated with nine oxygen atoms (seven
accurate. Moreover, in order to effectively distinguish various from four different completely deprotonated DPON 3- ligands,
molecules or ions, complex fluorescent signal combinations and two from coordinated water molecules), and forms a
generated by multi-fluorescent centers are needed. twisted tri-capped triangular prismatic geometry. The bond
Furthermore, the extensive sensing functions make multi- lengths of Eu–O bond range from 2.373(4) to 2.684(4) Å, typical
emission Ln-MOFs an important role in the club of “smart values of Eu(III)–carboxyl complexes.
materials”.22,37,38 The high surface areas result from the ordered The completely deprotonated DPON3- coordinate with four
pore structure can be utilized to preconcentrate analytes to Eu3+ ions through μ4- ƞ1: ƞ1: ƞ1: ƞ2: ƞ1: ƞ1 -bridging mode and the
realize efficient fluorescence recognition. Complex multi- dihedral angle between benzene ring and pyridine ring is
fluorescent outputs are also helpful for the construction of 77.119° (Fig. S1†). Two adjacent Eu3+ ions in the structure are
advanced logic circuits. With the more cost‐effective and facile connected by six carboxyl groups to form [Eu2(COO)6] secondary
operation process than DNA modification, Ln-MOFs molecular building units (SBUs). The [Eu2(COO)6] SBUs are linked to form
system becomes a promising candidate for logical devices. We one-dimensional chains along crystallographic a axis and b axis
believe that it will effectively combine analytes recognition and through carboxyl groups, respectively (Fig. S2†). Then the 2D
logic operation in the near future. framework is further constructed with a one-dimensional
Here, we report a series of Ln-MOFs channel (8.972×8.576 Å2) along the a axis (Fig. 1d). The 2D
{[Ln(DPON)(H2O)2]·(H2O)}n (Ln = Nd (1-Nd), Sm (2-Sm), Eu (3- framework can be simplified to a 3, 6-connected kgd network
Eu), Gd (4-Gd), Tb (5-Tb) and Dy (6-Dy)) and a microscale (Fig. 1c) and the final 3D structure are formed through C1-
heterometallic white light Ln-MOF (Eu0.059Tb0.051Gd0.89-DPON) H1B⋯π (2.898 Å) hydrogen bonding interactions (Fig. S3†).
that constructed of flexible ligand H 3DPON. Based on the highly Crystallographic data for Ln-MOFs are listed in Table S1†. Part
guests-depend emission of three emission centers (ligand: of the bond angles and bond lengths are listed in Table S2~S7†.
B415, Tb3+: G544, and Eu3+: R616) in Eu0.059Tb0.051Gd0.89-DPON, Furthermore, the results of FT-IR spectra, TG analysis and PXRD
it is fabricated to serve as a fluorescent platform for various patterns (Fig. S4, S5 and S6†) are in good agreement with the
toxic solvent molecules, cations and anions. With open metal results of single-crystal X-ray diffraction analysis.
sites and suitable channel, the Ln-MOF can not only efficiently
recognize formol in aqueous solution within 2  min (limit of
detection (LOD) is 0.0193 vol %), but achieve low-concentration
(1.592 mg/m3) formol detection in vapor. The first Ln-MOF
fluorescent probe for detecting VO43- is also constructed based
on the weak interaction between the guest anion and the
framework (LOD: 0.42 μM). The excellent fluorescence material
can effectively sense different solvent molecules and metal ions
through three-dimensional (3D) readouts by combining
different ratiometric emission intensities of three emission
centers. The outstanding specific surface area result from
micron size also improves detection efficiency. Moreover,
based on the fluorescence turn-on or quenching effect of
several contaminating ions (Fe3+, VO43-, and S2−) on the tri‐
emission fluorescence material, multicomponent recognition
has been achieved through a Boolean logic operation (Scheme Fig. 1. Crystal structure of 3-Eu. (a) asymmetric unit of 3-Eu with hydrogen atoms being
1). Compared to traditional single‐output logic circuits, the omitted for clarity. (b) The 2D framework of 3-Eu, where Eu3+ is represented as a
multiple outputs in our system can produce different logic polyhedron. (c) The view of the 2-D kgd network with {43}2{46·66·83} topology in 3-Eu
(Octahedron represents 6-connected [Eu2(COO)6] SUBs and triangle represents 3-
operations by the same analytes inputting, which can enlarge
connected ligands). (d) The 1D channel of the framework.
the information content in logic library and further improve the

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By adjusting the molar ratio of Ln3+ and the excitation wavelength,

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DOI: 10.1039/C8TC05968C
we obtained a suitable white light material whose intensities of three
emission centers are equal (Fig. 2). In order to confirm the actual
molar ratio of Eu3+, Tb3+ and Gd3+, ICP-MS analysis is carried out
(Table S8†) and the material is finally named Eu0.059Tb0.051Gd0.89-

Journal of Materials Chemistry C Accepted Manuscript

DPON. Eu0.059Tb0.051Gd0.89-DPON, whose structure is confirmed by
PXRD (Fig. S6†), is composed of regular quadrilateral and hexagonal
sheet-shaped crystal with the sizes of 1.3~2.8 μm and smooth
surface (Fig. 3). The 1D channel has a suitable size (8.972×8.576 Å2)
for the entry of cations, anions and small molecules. The three
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emission centers give the diversity of fluorescence responses to

analytes. Moreover, open metal sites give Eu0.059Tb0.051Gd0.89-DPON
affinity to some anions and negatively charged groups and thus make
it possible to produce various fluorescence responses through host-
guest interactions. Finally, high surface areas result from microscale
crystal would concentrate analytes to high levels, which can enhance
detective sensitivity. In addition, the stable structure and
Fig. 2. (a) Emission spectra of EuxTbyGd1-x-y-DPON excited at 321 nm. (b) CIE fluorescence performance of Eu0.059Tb0.051Gd0.89-DPON is proved by
chromaticity diagram of EuxTbyGd1-x-y-DPON (the ratio of Tb/Eu increases from A
to F), insets show the corresponding photograph. (c) 3D solid-state powder XRD patterns and quantum yields characterization (Fig. S6
photofluorescent spectrum of Eu0.059Tb0.051Gd0.89-DPON. (d) CIE chromaticity
diagram of Eu0.059Tb0.051Gd0.89-DPON with excitation wavelengths from 280 to 380 and Table S9†).
nm, insets show the white light photograph excited at 340 nm.
Sensing properties and fluorescent response mechanism
Photophysical properties It is understood that the fluorescent sensing of small
Herein, a series of Ln-MOFs are reported and their fluorescent molecules/ions through relative emission intensities of multi-
properties are investigated (Fig. S7 and S8†). All Ln-MOFs exhibited fluorescent centers probes is more reliable and accurate than single
sharp and well-separated characteristic emission bands. As for 3-Eu emission intensity. With three comparable emissions centers, the
and 5-Tb, under 321 nm excitation, no wide emission of ligand can white light Eu0.059Tb0.051Gd0.89-DPON is expected for fluorescent
be observed, which reveals effective sensitization on Eu3+ and Tb3+. detection.
To better understand the energy transfer process within 3-Eu and 5- Formol is one dangerous and widespread global pollutant which
Tb, the excited energy levels of ligand are established (Fig. S9†). Both has been paid great attention. It is noteworthy that when
the triplet excited-state energy (T1: 21053 cm−1) and singlet excited- Eu0.059Tb0.051Gd0.89-DPON (1 mg) was dispersed into formol (10 ml),
state energy (S1: 30395 cm−1) of ligand are calculated by the density the characteristic emission of both Eu3+ and Tb3+ are almost
functional theory (DFT) calculations at the B3LYP/6-31 G* level, and completely quenched (Fig. 4a). The quenching efficiency on Tb3+ has
are also confirmed by emission spectrum of 4-Gd at 77K and solid UV reached 91%. Generally, the luminescence quench of
absorption spectrum of H3DPON (Fig. S10†), respectively.39 The Eu0.059Tb0.051Gd0.89-DPON is possibly attributed to the following three
energy gap ΔE (1ππ*−3ππ*) of H3DPON is 9342 cm−1, larger than 5000 processes: (1) formol induced framework collapse of
cm−1. According to Reinhoudt’s empirical rule and Latva rule, the Eu0.059Tb0.051Gd0.89-DPON, (2) direct interaction between formol and
intersystem crossing (ISC) process in H3DPON is effective, and the Ln3+, and (3) formol interact with the ligand of Eu0.059Tb0.051Gd0.89-
emissions of both Eu3+ and Tb3+ could be sensitized. DPON.5
Firstly, the framework of Eu0.059Tb0.051Gd0.89-DPON remains in the
presence of formol as the PXRD patterns show in Fig. S6†. Then, in
order to judge if the interaction between formol and ligand exists,
the premises of photoinduced electron transfer (PET), Dexter
electron transfer (ET), and Förster resonance energy transfer (FRET)
mechanism are investigated. In general, the main driving force of PET
process is the energy gap between the lowest unoccupied molecular

Fig.3. SEM images of Eu0.059Tb0.051Gd0.89-DPON, (a) quadrilateral and (b) hexagonal. Scale
bar = 1 μm. (c) PXRD patterns of 1-Nd ~ 6-Dy and Eu0.059Tb0.051Gd0.89-DPON. (d) Dynamic Fig. 4. Fluorescence response of Eu0.059Tb0.051Gd0.89-DPON toward (a) formol and (b) VO43-
light scattering (DLS) characterization of Eu0.059Tb0.051Gd0.89-DPON. , Fe3+ and S2− (1 mM).

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orbitals (LUMO) of donor and acceptor, and the LUMO energy level Similar with Fe3+, VO43- has also became the important factor
View Article of
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of donor should be higher than that of acceptor when PET act as the water pollution due to its wide application inDOI: 10.1039/C8TC05968C
the industries. Different
luminescence quenching mechanism.40 However, an opposite result to the quenching effect, the unique emission spectra of VO43- treated
is obtained from LUMO energy levels of ligand (donor) and formol Eu0.059Tb0.051Gd0.89-DPON attracted our attention. The emission
(acceptor) calculated by DFT at the B3LYP/6-31 G* level (Fig. 5b and intensities of the ligand and Tb3+ abruptly decreased and even

Journal of Materials Chemistry C Accepted Manuscript

Table S10†), which indicates the absence of the PET process. Similarly, disappeared, while the emission intensity of Eu3+ exhibited a 2.5 fold
the ET mechanism is also excluded due to the higher T 1 energy level significant enhancement (Fig. 4b). Moreover, the fluorescence
of acceptor (24109 cm−1) than donor (21053 cm−1). As for FRET lifetime of Tb3+ and Eu3+ also meet this trend (Fig. S13 and Table
process, there is no obvious overlap between UV-vis spectrum of S11†).
formol and emission spectrum of ligand (Fig. S11 †). Therefore, the The mechanism for the fluorescent response of
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absence of the interaction between formol and ligand is confirmed Eu0.059Tb0.051Gd0.89-DPON caused by VO43- is also investigated in
by the above results. Moreover, as formol has available functional detail. Firstly, the framework integrity is evidenced by the same PXRD
group (=C=O), the binding energy of Ln3+ reduced in the X‐ray patterns of Eu0.059Tb0.051Gd0.89-DPON before and after treated by
photoelectron spectroscopy (XPS) spectra with the present of formol VO43-. Then, as the characteristic emission intensity of Eu3+ relies on
as expected (Fig. S12†), indicating the interaction between formol the efficiency of “antenna effect”.44 Hence, the mechanism of
and Ln3+. Therefore, the fluorescence quench of Ln3+ attributes to its fluorescence enhancement at 616 nm may be proposed that VO 43-
interaction with carbonyl in formol. Considering the unchanged can facilitate the efficiency of energy transfer from ligand to Eu3+.
fluorescence lifetime of Ln3+ (Table S11†), the fluorescent quenching However, the absence of available functional groups in ligand
process belongs to a static mechanism.11 excludes the possibility of the interaction of VO43- and ligand.
It is known to all that Fe3+ ion plays an important role in both In addition, considering the situation of energy transfer directly
industrial process and biological systems. However, a lower or higher from VO43- to Eu3+,45-47 the possibility of the interaction of VO43- and
concentration of Fe3+ can seriously affect human health and Ln3+ is investigated. As the XPS spectra shows (Fig. S12†), the Ln3d
environmental safety.41-43 Therefore, the detection of Fe3+ is an bonding energy make an obvious decrease after treated by VO43- ion.
important part of water monitoring. As Eu0.059Tb0.051Gd0.89-DPON (1 Therefore, a coordination effect between VO 43- and Ln3+ can be
mg) was treated with into Fe3+ aqueous solution (1 mM), the speculated. The significant changes in fluorescence lifetime of Eu3+
emissions of Eu3+, Tb3+ and ligand are all quenched (Fig. 4b). and Tb3+ also prove this interaction. In order to find out the reason
The first, after treated by Fe3+, the PXRD pattern of for different effects on Eu3+ and Tb3+ caused by VO43-, the excited-
Eu0.059Tb0.051Gd0.89-DPON is consistent with the original one, which state energy of ligand and VO43- are discussed. From the perspective
deny the possibility of Eu0.059Tb0.051Gd0.89-DPON framework collapse of energy level, the emission bond 3-Gd at 77K has an apparent
(Fig. S6†). Secondly, the framework integrity (Fig. S6†) and short bathochromic shift (from 475 to 515 nm) after treated by VO 43- (Fig.
response time (about 30s) deny the occurrence of ion exchange S14†) and the new triplet excited-state energy (T1) of VO43- is
between Fe3+ and Ln3+.15 The last, as Fe3+ has strong absorption calculated to be 19417 cm-1, which lies between 5D4 level of Tb3+
capacity in the ultraviolet region, a competitive energy absorption (20500 cm-1) and 5D0 level of Eu3+ (17300 cm-1). As the energy level
process between Fe3+ and organic ligand can be speculated. By diagram (Fig. 5a) shows, the VO43- T1 level is suitable for Eu3+ rather
comparing the absorption performance of Fe3+ and than Tb3+. Moreover, the fluorescence lifetime and intensity
Eu0.059Tb0.051Gd0.89-DPON, we find an obvious spectral overlap reduction of Tb3+ can be attributed to the competitive absorption
between the UV-vis absorption spectra of Fe3+ and between VO43- and Eu0.059Tb0.051Gd0.89-DPON that proved by the
Eu0.059Tb0.051Gd0.89-DPON (Fig. S11†). Therefore, excited energy obvious overlap of their UV-vis absorption spectrum (Fig. S11†).
effectively absorbed by Fe3+ leads to the decrease efficiency of Similarly, the lower π* energy level of VO43- than ligand also can be
“antenna effect” and finally cause the fluorescent quenching.15 proved by UV-vis absorption spectrum (Fig. S10 and S11†) (375 nm
of VO43- compared to 329 nm of ligand). As a result, the energy
transfer from VO43- to Eu3+ cause the turn-on fluorescence response
at 616 nm and the competitive absorption ability of VO43- quench the
emission of Tb3+.
As for S2-, being an important anion for biologically and
environmentally, it is widely used in industry. However, because of
its toxicity to human body, and corrosiveness to construction, S2-
becomes an important analyte for water monitoring.56 Similar with
formol, S2- induced the quenching effect on both Eu3+ and Tb3+, while
the emission of ligand remains (Fig. 4b). Seen from the PXRD patterns
(Fig. S6†), the diffraction peak of Eu0.059Tb0.051Gd0.89-DPON
disappears and the crystallinity decreases after treated by S2-, the
framework collapse of Eu0.059Tb0.051Gd0.89-DPON induced by S2- can
Fig. 5. Sensing mechanism of VO43- and formol. (a) Simplied schematic diagram of
competitive absorption process between VO43- and ligand. (b) Schematic representation
be confirmed.
of electronic cloud orbit distributions of ligand H 3DPON, formol, acetaldehyde and Fluorescent probe detection for formol
acetone. (c) The schematic illustration of the mechanism of VO43- and formol sensing by In view of the serious harm of formol to human, the detection of
Eu0.059Tb0.051Gd0.89-DPON. formol is meaningful for water monitoring. As formol contains

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carbonyl group that could induce fluorescent response through host- View Article Online
guest interactions, it is feasible to develop Eu0.059Tb0.051Gd0.89-DPON DOI: 10.1039/C8TC05968C
as a fluorescence probe for formol.
Formol was diluted into aqueous solution of different contents
(vol %) and soaked with Eu0.059Tb0.051Gd0.89-DPON. Taking the

Journal of Materials Chemistry C Accepted Manuscript

emission intensities of Tb3+ as reference, we find that fluorescent
quenching efficiency of Tb3+ in response to formol can be
quantitatively explained in the content range of 0 – 30 vol % by the
Stern−Volmer (SV) equation: I0/I = KSV[Q] + 1, where I0 and I are the
luminescence intensities at 544 nm before and after adding formol,
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respectively, KSV is the quenching constant, and [Q] is the formol

volume content in aqueous solution. As illustrated in Fig. 6b, the SV
curve for formol is well fitted linear (R2 = 0.99842) with the KSV value
of 0.33504 vol %-1. In addition, the LOD is calculated to be 0.0193 vol
% (Table S12†), which is comparable or even better than those of the
formerly reported MOF-based formol sensor materials.8,48,49
When expanded into practical application, the response time and
recyclability of Eu0.059Tb0.051Gd0.89-DPON are important parameters
that must be considered. After the addition of formol (22.8 vol %),
the fluorescence emission intensities at 544 nm is recorded per 30 s
until it becomes stable (Fig. S15†). Consequently, Eu0.059Tb0.051Gd0.89-
DPON exhibits a rapid response (2 min) for formol. On the other
hand, the recyclability of Eu0.059Tb0.051Gd0.89-DPON is investigated
through the cycle experiment (Fig. 6d and S16†). After detection of
formol, the suspension is centrifuged and washed several times with Fig. 6. (a) Emission spectra of Eu0.059Tb0.051Gd0.89-DPON with the increasing
ethanol as well as distilled water under ultrasonic. contents (0–30 vol % in aqueous solution) of formol. (b) The SV plots of
Eu0.059Tb0.051Gd0.89-DPON, insets show the corresponding photograph. (c) Simple
Eu0.059Tb0.051Gd0.89-DPON exhibits stable fluorescence quenching device for providing and detecting formol atmosphere. (d) Fluorescence
intensities at 544 nm of Eu0.059Tb0.051Gd0.89-DPON during five consecutive
and recovery caused by the addition and removal of formol, quenching and regenerating cycles. (e) Fluorescence response of
Eu0.059Tb0.051Gd0.89-DPON treated by different organic solvents for 30 min with 340
respectively. Furthermore, the framework integrity evidenced by the nm excitation. (f) The 3D decoded map for various solvent molecules based on the
ratios of I544/I491, I616/I592 and I415/I544.
PXRD patterns also prove the well recyclability of Eu0.059Tb0.051Gd0.89-
DPON for formol detection. As formol is a volatile organic solvents could be put in a highly differentiated 3D decoded map (Fig.
compounds (VOC) that can cause cancer, we designed a simple 6f). Obviously, the coordinate of each solvent molecule is unique and
device and achieved formol detection in air at a low concentration even structurally similar substances could be easily distinguished in
(1.592 mg/m3) (Fig. 6c, S17 and S18†). this 3D decoding map (Fig. 6f), such as CH2Cl2 (2.18, 3.17, 1.21) and
Finally, the sensor is required to have good selectivity to the CH3Cl (2.05, 3.75, 0.48). Thus, different solvents can be easily
sensing objectives. In this work, the Eu0.059Tb0.051Gd0.89-DPON (1 mg) distinguished and recognized by the 3D decoded map. Moreover,
was dispersed into different kinds of solvents (10 ml), respectively when we change the contents of DMF, DMSO or EtOH to 30 vol% and
and the emission spectra were recorded under 340 nm excitation. As 50 vol, their coordinates only change slightly (Fig. S19†).
shown in Fig. 6e, Eu0.059Tb0.051Gd0.89-DPON exhibit obvious solvents- Inspired by the solvent-dependent emission of Eu0.059Tb0.051Gd0.89-
dependent emission: various solvents exhibited different degrees of DPON, we extend its application to cations detection. In this work,
quenching effect on Eu0.059Tb0.051Gd0.89-DPON. For example, in these 19 kinds of cations were chosen for detection and they all could be
14 kinds of solvent: only formol shows a completely quenching effect distinguished easily through the 3D decoded map proposed above
at both 545 nm and 615 nm. A moderate quenching effect mainly on (Fig. S20†).
the emissions of Tb3+ is induced by CHCl3 and DMA, while the Fluorescent Probe Detection for VO43-
remaining CH2Cl2, benzene, EtOH, DMF, CH3CN, paraxylene, MeOH, So far, many luminescent probes of small molecules/cations (such
methylbenzene, cyclohexane, CH3COOH and formol showed a as nitro-compounds, explosive, Co2+, Cu2+, etc.) based on Ln-MOFs
gradually enhanced quenching effect both on the emission of Tb3+ have been successfully synthesized.52-55 However, the detection for
and Eu3+. Obviously, the solvent molecules not only can effectively pollutant anions are rarely reported, especially for VO43-. In view of
tune the energy transfer efficiency from ligand to Ln3+ in the fluorescence turn-on response to VO43-, the Eu0.059Tb0.051Gd0.89-
heterometallic Ln-MOF, but also modulate the energy allocation DPON used as first fluorescent probes for VO43- is meaningful for
between Eu3+and Tb3+ in heterometallic Ln-MOF.15,27,50,51 human health and environmental monitoring.
3D decoded map
To confirm the feasibility of Eu0.059Tb0.051Gd0.89-DPON for the
Since every solvent molecule shows different capabilities on detection of VO43- ion, we measured a series of fluorescence
turning “antenna effect” efficiency in the luminescence process, it is responses of Eu0.059Tb0.051Gd0.89-DPON to different concentrations of
convenient and accurate to distinguish these solvents by the VO43- ion. Interestingly, we find a linear relationship (Fig. 7b)
emission intensities ratios of different emission centers. All of these between emission intensity ratio (I616/I544) and concentration of VO43-

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within the range of 0 − 0.2 mM: I616/I544 = 0.85871 + 4.55968 cNa3VO4 The selectivity to the VO43- is also investigated. Take metal
View ArticleNa as
Online
(R2 = 0.99863). The LOD toward VO43- is calculated to be 0.42 μM an example, 11 kinds of sodium metal saltsDOI: (1 10.1039/C8TC05968C
mM) with different
(Table S13†) through the equation: LOD = k × σ/S. Where k is the anions were added into Eu0.059Tb0.051Gd0.89-DPON aqueous solution,
confidence level parameter and k = 3 at the 99% confidence level, σ respectively. According their emission spectra recorded in Fig. 7e,
is the standard deviation for five times repeated detections of blank except for very few anions, most anions exhibit weak impact on the

Journal of Materials Chemistry C Accepted Manuscript

solutions, and S is the slope of the calibration curve. emission of Eu0.059Tb0.051Gd0.89-DPON. Only the VO43- shows a
Moreover, the response time and recyclability of significant enhancement on Eu3+. The emission spectra of NO3-, SCN-
Eu0.059Tb0.051Gd0.89-DPON is also investigated. After the addition of , HSO3-, S2O32-, SO42-, CH3COO-, Cl-, NO2- are almost the same as the
Na3VO4 (1 mM), the emission intensities of Eu3+ and Tb3+ is recorded control one (Free). Their 3D coordinates (I544/I491, I616/I592, I415/I544)
every 30s until they become stable (Fig. S21†). It is worthy to note are in a very small area around Na+ (2.26, 3.75, 0.47) and do not
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that Eu0.059Tb0.051Gd0.89-DPON shows a short response time of 1.5 overlap with other cationic regions (Fig. S23†), which implies that it
min (Fig. 7c), which endow Ln-MOF the possibility for convenient is accurate to determine the cation with 3D coordinates.
practical application. In the cycle experiment (Fig. 7d and S22†), we Furthermore, in order to utilize the Eu0.059Tb0.051Gd0.89-DPON into
find that the ratio of I616/I544 always stay above 10 in the presence of VO43- detection practically, the influence of several competing anions
VO43- (2 mM) during the five times cycling process. Every time after on the fluorescence responses for VO43- ion was evaluated (Fig. S24).
detection of VO43-, suspensions are centrifuged and washed several As shown in Fig. 7f, the recognition and sensing properties for VO 43-
times with ethanol as well as distilled water under ultrasonic. And ion still remains in the presence of different anions and even 3, 5, 7
the ratio of I616/I544 drops back to around 0.9 through the simple and 9 kinds of interference anions, which indicates the high
process of ultrasonic washing. This apparent change of I616/I544 still selectivity of Eu0.059Tb0.051Gd0.89-DPON.
remains after five continuous cycles. Meanwhile, the unchanged Construction of boolean logic operation and water monitoring
PXRD patterns of the finally recycled Eu0.059Tb0.051Gd0.89-DPON
reveals its well retained framework (Fig. S6†). High selectivity, fast Based on the selective analysis performance of Eu0.059Tb0.051Gd0.89-
response and recyclability together endow Eu0.059Tb0.051Gd0.89-DPON DPON toward Fe3+, VO43-, and S2-, we design a fluorescence logic
turn-on ratiometric probe with promising practical applications. system to achieve the multiplexed analysis of the two and even three
ions. In the Boolean logic operation, Eu0.059Tb0.051Gd0.89-DPON serve
as gate, while the analyzed substances (Fe3+, VO43- or S2-) and
fluorescence emission intensities at 415 nm (B415), 544 nm (G544)
and 616 nm (R616) are set as inputs and outputs, respectively. The
input is “on” (i.e., 1) when the analyzed substances exist, otherwise
it is “off” (i.e., 0). The output is defined by comparing with a threshold
value (B415: 0.5, G544: 1 and R616: 1.5) which depends on the
fluorescence intensities of different emission centers, higher than
the threshold value outputs 1, while lower outputs 0. So, based on
this logic operation, three outputs could be obtained with two or
three inputs. Subsequently, we construct a series of logic operations
(NOR, IMP, NOT) driven by two inputs (Fe3+ + VO43-, Fe3+ + S2-, and
VO43- + S2-).

Fig. 7. (a) Emission spectra of Eu0.059Tb0.051Gd0.89-DPON with the increasing

concentrations (0 – 0.2 mM) of Na3VO4. (b) Concentration dependence of fluorescence
intensity ratios of I616/I544 in the range of 0 – 0.2 mM, insets show the corresponding
photograph. (c) Fluorescence response for VO43- (I616/I544) in 0 - 6 minutes after the
addition of Na3VO4. (d) Fluorescence intensity ratios of I616/I544 during five consecutive Fig. 8. Truth tables of the double inputs Boolean logic gates (a) Fe3+ + VO43-, (d) Fe3+ + S2-
enhancement and regeneration cycles. (e) Fluorescence response of Eu0.059Tb0.051Gd0.89- and (g) VO43- + S2-. Column diagrams of the fluorescence intensities of B415, G544, and
R616 in the double inputs of Boolean logic gates (b) Fe3+ + VO43-, (e) Fe3+ + S2- and (h)
DPON toward different anions (1 mM aqueous solution for 30 min) excited at 340 nm.
VO43- + S2-, the dashed lines represent the thresholds (B415: 0.5, G544: 1 and R616: 1.5).
(f) Fluorescence responses for VO43- in the presence of one or more anions (λex = 340 Electronic equivalent circuitries of the double inputs Boolean logic gates (c) Fe3+ + VO43-,
nm). (f) Fe3+ + S2- and (i) VO43- + S2-. The concentration of each input is 1 mM.

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third ions as input to logical system and two new logical Viewoperations
Article Online
(XOR, INH) generated based on a new threshold DOI: 10.1039/C8TC05968C
(B415: 0.5, G544: 1
and R616: 2) value. The corresponding emission spectra are also
shown in Fig. 4b and S25†. A XOR logic operation outputs 1 at 1/0 or
0/1 input, while INH logic operation has the turn‐on output only at

Journal of Materials Chemistry C Accepted Manuscript

one particular input. Seen from Fig. 9b, when B415 is used as the
output signal, the first INH gate is constructed with VO43- and S2-
double inputs and its output is integrated with the Fe3+ to form the
new input for the second NOR gate. The G544 input still belongs to
NOR logic operation since the identical quenching effect of three
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ions, only the 0/0/0 input could produce 1 input. As for emission at
616 nm (R616), after the NOT logic operation, the Fe3+ input is
integrated into the next XOR logic operation with S 2- input.
Moreover, in the presence of all three inputs (1/1/1), Fe3+ lost its
function through excess connection with VO43- and S2-, while the
remaining VO43- and S2- make their own effects on
Eu0.059Tb0.051Gd0.89-DPON, resulting in the 1/0/1 output. The
integration of complex logic evolution network with three inputs
(Fe3+, VO43- and S2-) and three outputs (B415, G544, and R616) is
revealed in Fig. 9d, which exhibits the powerful molecular
recognition ability of Eu0.059Tb0.051Gd0.89-DPON fluorescence system.
Fig. 9. (a) Column diagram of fluorescence intensities of B415, G544, and R616:
The above logic operations mainly described the functions of each
the dashed lines show the thresholds (B415: 0.5, G544: 1 and R616: 2). (b) input and their interactions, do not take their order into
Electronic equivalent circuitry of the three inputs Boolean logic gate. (c) Truth
table of the three inputs Boolean logic gate. (d) Compound logic circuit with three consideration. Then the varied orders of three inputs (Fe3+, VO43- and
inputs and two outputs fluorescence signal (blue shadow represents the
fluorescence of B415 and red shadow represents the fluorescence of R616). (e) S2-) were complied to obtain different inputs (Fig. S26†). As S2- takes
Column diagram of fluorescence intensities of B415, G544, and R616: the dashed
lines show the thresholds (R616: 2 and B415: 0.5). (f) The password lock security some time to destroy the framework, each operation lasts for 3 hours
system with different input sequences. (A, B and C represent Fe 3+, VO43-, and S2−,
respectively). before proceeding with other operations to ensure that they make
fully effect on Eu0.059Tb0.051Gd0.89-DPON. As shown in Fig. 9e, the
As we all know, NOR logic operation produces an output of 1 only emission at 415 nm outputs 1 in A (Fe3+), B (VO43-), C (S2-) and B, A, C
when all inputs are 0. As demonstrated in Fig. 8b, 8e and 8h, the sequence. Only the A, C, B sequence make the turn-on output of
fluorescence intensities at 544 nm exceeded threshold (G544: 1) only R616 since the connection of Fe3+ and S2- retain the complete
in the absence of Fe3+, VO43- and S2-, otherwise it outputs 0. Similarly, framework. The sequence-depend output characteristics inspired us
identical NOR logic operation can be also implemented on the B415 to develop the logic operation into a simple password lock (Fig. 9f).
output of Fe3+ + VO43- double inputs logic gate and the R616 output Blue (B415) and red (R616) emissions are defined as alarm and
of Fe3+ + S2- logic gate (Fig. 8b and 8e). The R616 output of Fe3+ + VO43- unlock, respectively, while the 0/0/0 output represents the lock.
double inputs logic gate belongs to the binary IMP logic operation Obviously, in addition to the correct password (A, C, B), other
which produces 0 output only at one particular input (1/0). When passwords can not open the lock, and even some wrong passwords
Fe3+ added alone, it exhibits great quenching effect on the emission (A, B, C and B, A, C) will trigger an alarm, which greatly enhances the
at 616 nm, while on the addition of VO43- (input: 1/1), most Fe3+ are security of the password lock.
combined to form a precipitate (Equation 1) and the remaining VO43-
are reactive.
Fe3+ + VO43- → FeVO4 ↓ (1) Conclusions
As shown in Fig. 8h, IMP logic operation can also be implemented on In summary, we have developed a “smart” tri‐emission white
B415 output when VO43- + S2- act as double inputs. This is because fluorescence material‐Eu0.059Tb0.051Gd0.89-DPON based on the
the framework collapse mechanism of S2-, which makes the VO43- live facile and cost‐effective method of in-situ Ln3+ heterometallic.
in silence when added together. Moreover, as Fe2S3 is also a Based on the specific fluorescence enhancement and quenching
precipitated substance (Equation 2), Fe3+ will greatly limit the response of VO43- and formol, respectively, we achieved fast
function of S2- in Fe3+ + S2- logic gate and form a NOT logic operation quantitative fluorescence detection of formol (LOD: 0.0193 vol
between Fe3+ input and B415 output. %) and VO43- (LOD: 0.42 μM) in aqueous solution. Also,
Fe3+ + S2- → Fe2S3 ↓ (2) detection of formol at low concentration (1.592 mg/m3) in air is
NOT logic operation also exist in VO43- + S2- logic gate. With the realized by using a designed device. Moreover, a novel 3D
addition of S2-, the characteristic emission of Eu3+ disappears and decoded map has been designed that can effectively and
thus R616 outputs 0. The corresponding fluorescence emission reliably distinguish different solvent molecules and metal ions
spectra of each logic gate are given in Fig. 4b and S25†. in aqueous solution. Finally, we constructed a Boolean logic
The aforementioned double input logic gate showed that operation based on the different fluorescence responses of the
Eu0.059Tb0.051Gd0.89-DPON, Fe3+, VO43- and S2- can self‐assemble and three illuminating centers to the contaminated ions (Fe3+, VO43-
interact with each other in aqueous solution. Then, we introduce the and S2-) in water, and thus realized the analysis of multi-

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components, which provides more opportunities for the 27 J. Zhou, H. Li, H. Zhang, H. Li, W. Shi and P. Cheng, Adv. Mater.
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29 B. B. Chen, Y. Yang, F. Zapata, G. Lin, G. Qian and E. B.
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Journal of Materials Chemistry C Accepted Manuscript

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This work was supported by National Natural Science
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33 G. W. Xu, Y. P. Wu, W. W. Dong, J. Zhao, X. Q. Wu, D. S. Li and

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DOI: 10.1039/C8TC05968C

Table of Contents Entry

Functional Microscale Single-phase White Emission

Journal of Materials Chemistry C Accepted Manuscript

Lanthanide MOF for Tunable Fluorescent Sensing and
Water Quality Monitoring
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Tiancheng Sun, Ping Wang, Ruiqing Fan*, Wei Chen, Sue Hao and Yulin Yang*

The “smart” fluorescence material‐Eu0.059Tb0.051Gd0.89-DPON contains functions of

multicomponent recognition, detection for formol / VO43- and analysis of
multi-components in water.