molecules
Review
Advance Progress on Luminescent Sensing of Nitroaromatics by
Crystalline Lanthanide–Organic Complexes
Yixia Ren 1, * , Zhihu Ma 1 , Ting Gao 1 and Yucang Liang 2, *
Citation: Ren, Y.; Ma, Z.; Gao, T.;
Liang, Y. Advance Progress on
Luminescent Sensing of
Nitroaromatics by Crystalline
Lanthanide–Organic Complexes.
Molecules 2023, 28, 4481. https://
doi.org/10.3390/molecules28114481
Academic Editor: Xiongfei Zhang
Received: 29 April 2023
Revised: 27 May 2023
Accepted: 29 May 2023
Published: 1 June 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Molecules 2023, 28, 4481. https://doi.org/10.3390/molecules28114481
1 Laboratory of New Energy and New Function Materials, Shaanxi Key Laboratory of Chemical Reaction
Engineering, College of Chemistry and Chemical Engineering, Yan’an University, Yan’an 716000, China;
mazhihu123@163.com (Z.M.); 13636869137@163.com (T.G.)
2 Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18,
72076 Tübingen, Germany
* Correspondence: renyx@yau.edu.cn (Y.R.); yucang.liang@uni-tuebingen.de (Y.L.)
Abstract: Water environment pollution is becoming an increasingly serious issue due to industrial
pollutants with the rapid development of modern industry. Among many pollutants, the toxic and
explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental
pollution of soil and groundwater. Therefore, the detection of nitroaromatics is of great significance
to environmental monitoring, citizen life and homeland security. Lanthanide–organic complexes
with controllable structural features and excellent optical performance have been rationally designed
and successfully prepared and used as lanthanide-based sensors for the detection of nitroaromatics.
This review will focus on crystalline luminescent lanthanide–organic sensing materials with different
dimensional structures, including the 0D discrete structure, 1D and 2D coordination polymers and the
3D framework. Large numbers of studies have shown that several nitroaromatics could be detected by
crystalline lanthanide–organic-complex-based sensors, for instance, nitrobenzene (NB), nitrophenol
(4-NP or 2-NP), trinitrophenol (TNP) and so on. The various fluorescence detection mechanisms were
summarized and sorted out in the review, which might help researchers or readers to comprehensively
understand the mechanism of the fluorescence detection of nitroaromatics and provide a theoretical
basis for the rational design of new crystalline lanthanide–organic complex-based sensors.
Keywords: lanthanide–organic complex; luminescent material; luminescence sensing; nitroaromatics;
mechanism
1. Introduction
Following the rapid development of modern industry, domestic wastewater, agricul-
tural wastewater and pharmaceutical wastewater contain more and more pollutants, such
as metal cations, anions, antibiotics, pesticides, nitro aromatic compounds and so on, which
are making water environmental pollution more and more serious [1–3]. Among these
pollutants, the toxic and explosive nitroaromatic compounds are often used as the starting
materials for the preparation of dyes and explosives in the chemical industry. It should be
noted that highly toxic nitroaromatics are extremely difficult to be degraded due to their
structural and chemical stability. For example, nitrobenzene (NB) is the simplest and small-
est molecule in nitroaromatics, which is often used as the intermediate and raw materials
for the productions of dyes, fragrances, explosives and other aniline products in the organic
synthesis industry. Inhalation of toxic NB vapor or skin contamination can cause acute
poisoning, headache, nausea, vomiting and so on [4–6]. Furthermore, 4-Nitrophenol (4-NP)
is mainly used as an intermediate in pesticide, pharmaceuticals, dyes and other fine chemi-
cals [7,8]. In addition, 2,4,6-trinitrophenol (TNP), as the main component of explosives and
gunpowder, is commonly used in the manufacture of dyes, preservatives and medicines.
Wastewater from these industries needs to be monitored and treated to prevent environ-
mental pollution [9,10]. Especially, high physiologically toxic nitroaromatics are harmful to
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Molecules 2023, 28, 4481 2 of 21

(ground)water, soil resources and human health when released into the environment. There-
fore, the detection of nitroaromatic compounds is of great significance to environmental
monitoring, citizen safety and homeland security [11–15]. At present, the analytical meth-
ods for detecting harmful substances in the environment mainly include atomic absorption
spectroscopy [16], mass spectrometry [17], optical gas chromatography-mass spectrom-
etry [18], gas chromatography-electron capture detection [19], surface-enhanced Raman
spectroscopy [20,21], X-ray imaging [21], thermal neutron analysis [21], electrochemical
procedures [20] and ion mobility spectroscopy (IMS) [20,21] and molecularly imprinted
polymers (MIPs) [22]. Note that fluorescence detection is a simple, convenient, highly sen-
sitive method for monitoring pollutants in wastewater [23–25] and vapor phases [26–28],
and even in commercial honey samples [29]; no special instructions are required compared
with other methods, while rapid and real-time detection is provided, and fluorescence
detection has demonstrated good sensitivity and selectivity.
Lanthanide ions have high coordination numbers and poor stereochemical prefer-
ences, sharp characteristic emission in the visible and near-infrared (NIR) ranges, large
antenna-induced offsets and long lifetimes. Lanthanide–organic complexes have been
widely investigated and applied in catalysis, adsorption, detection, luminescence, mag-
netism, separation, and so on [30–32]. In particular, lanthanide–organic complexes have the
advantages of good luminescence performance, long emission lifetime, large Stokes shift
and high quantum yield, and have broad application prospects in the field of fluorescence
sensing [33,34]. It is well known that lanthanide complexes have a unique luminescence
process, and the interaction between Ln3+ and an organic ligand coordinated to the Ln
center with a fluorescence-sensing analyte can affect their emission intensity. Due to their
unique properties, high coordination numbers and the flexible coordination modes of lan-
thanide metal ions, lanthanide–organic complexes possess diverse structures and excellent
properties, in which the luminescence performance mainly stems from the metal-centered
luminescence generated by absorbing radiative excitation energy from the excited state.
The lanthanide ions regularly fill electrons in the 4f orbital, and the electron configuration
is [Xe]4fn (n = 0–14). The electronic structure generates well-defined energy levels, leading
to interesting luminescent properties. The 4f orbital is insensitive to the outer electrons
because it’s well shielded by the 5s and 5d shells. In addition, f-f transitions are forbid-
den, providing sharp, narrow, and iconic emission peaks. Lanthanide ions have a narrow
absorption cross section and limited absorption efficiency, making it difficult to directly
emit light through photoexcitation. This problem is solved by the “antenna effect”, which
mainly realizes the luminescence of lanthanide–organic complexes by transferring energy
to lanthanide ions through organic ligands. The “antenna effect” refers to the formation of
Ln–organic complexes through coordination bonds between lanthanide ions and organic
ligand molecules with a high light-absorption coefficient [35]. With the help of the large
absorption of the organic ligand in the ultraviolet region, the characteristic emission of
lanthanide ions is greatly improved, and its energy is transferred to the emission level of
lanthanide ions through an efficient intramolecular energy-transfer process.
As shown in Figure 1, the specific process of energy absorption and conversion of
lanthanide–organic complexes is embodied in three steps: First, the ground-state organic-
ligand chrominance group in the lanthanide coordination polymer absorbs the excitation
light and is excited from the ground state (S0 ) to the first excited singlet state (S1 ), and the
excited electrons return to the ground state by radiation or non-radiation means, or the first
singlet state (S1 ) can shift the system to the triplet excited state (T1 ). Finally, the T1 state
of the ligand is transferred to the metal ion, resulting in the highly sensitive luminescence
of the lanthanide ion. Subsequently, the energy of the lanthanide ion decreases from the
excited state to the ground state, and the characteristic fluorescence of the lanthanide ion
is emitted. However, the energy transfer from ligands to lanthanide ions is incomplete,
and the intramolecular transfer of ligands exists in the form of radiation (π-π*, n-π*). Most
lanthanide coordination polymers exhibit the characteristic emission colors of lanthanide
Molecules 2023, 28, x FOR PEER REVIEW 3 of 22

Molecules 2023, 28, 4481 ion is emitted. However, the energy transfer from ligands to lanthanide ions is incomplete, 3 of 21
and the intramolecular transfer of ligands exists in the form of radiation (π-π*, n-π*). Most
lanthanide coordination polymers exhibit the characteristic emission colors of lanthanide
metal ions,
metal ions, such
suchas Tb3+3+,, Tm
asTb Tm3+ 3+, Eu3+
3+ and Sm3+
and 3+, , which
which are
are green, blue, red
red and
and orange,
orange, re-
spectively, while
respectively, whileNd 3+
Nd , ,Yb
3+ 3+
Yb and
3+ andEr 3+
Er emit
3+ emitininthe
thenear
nearinfrared
infrared region [36].
region [36].

Figure1.1.Process
Figure Processofof energy
energy absorption
absorption and and conversion
conversion of Tb(III)/Eu(III)
of Tb(III)/Eu(III) complexes.
complexes. (ISC: intersys-
(ISC: intersystem
tem crossing;
crossing; IET: intramolecular
IET: intramolecular energyenergy transfer;
transfer; BET:
BET: back backtransfer).
energy energy transfer).

The
The diversity
diversityofoforganic
organicligands
ligandsmakesmakes Ln–organic
Ln–organic complexes
complexes exhibit different
exhibit re- re-
different
sponses to different fluorescence-sensing analytes, and, hence, Ln–organic
sponses to different fluorescence-sensing analytes, and, hence, Ln–organic complexes are complexes are
expected
expected to tobe beefficient
efficientandandmultifunctional
multifunctionalfluorescence-sensing
fluorescence-sensing materials
materials [37–39].
[37–39].AsAs a
a fluorescence-sensing material, Ln–organic complexes indicate some potential advan-
fluorescence-sensing material, Ln–organic complexes indicate some potential advantages:
tages: (1) the diversity of functional ligands with different molecular sizes ensures that
(1) the diversity of functional ligands with different molecular sizes ensures that the pre-
the prepared Ln–organic complexes are suitable for the requirements and goals of the
pared Ln–organic complexes are suitable for the requirements and goals of the detection
detection of analytes; (2) the pore characteristics of Ln–organic complexes are conducive to
of analytes;
the adsorption (2)ofthe pore characteristics
analytes and the increaseofinLn–organic complexesmaking
analyte concentration, are conducive
them closer to the
to ad-
sorption of analytes and the increase in analyte concentration, making
the host–guest interaction sites and decreasing the low detection limit of the analytes; and them closer to the
(3) the high specific surface area of Ln–organic complexes can enrich the analyte and im- (3)
host–guest interaction sites and decreasing the low detection limit of the analytes; and
the high
prove thespecific
sensitivitysurface area of Ln–organic
of detection. Moreover, sensorscomplexes can enrich
prepared the analyte
with Ln–organic and improve
complexes
the sensitivity
also have specialofadvantages:
detection. Moreover,
(1) compared sensors prepared with Ln–organic
with high-performance complexes also
liquid chromatography
haveatomic
and special advantages:
absorption (1) compared
spectrometry, they are with
easyhigh-performance
and convenient to operateliquid and chromatography
low-cost,
and
and there
atomic is no special requirement
absorption spectrometry, for they
the instruments;
are easy and(2)convenient
the flexibletoporosity
operatelimitsand low-
the
cost,distance
and there between the analyte
is no special and the complex,
requirement ensuring the
for the instruments; (2)interaction
the flexible between
porosity the limits
complex and the analyte; and (3) the interaction site of the object is
the distance between the analyte and the complex, ensuring the interaction between the easy to identify, and the
sensing
complexmechanism is easy and
and the analyte; to infer andinteraction
(3) the elucidate. Basedsite ofon the
the abovementioned
object advan- and
is easy to identify,
tages, Ln–organic complexes are widely applied in the detection
the sensing mechanism is easy to infer and elucidate. Based on the abovementioned ad- of metal cations, anions,
nitro-aromatic compounds, antibiotics, pesticides, volatile organic compounds, biological
vantages, Ln–organic complexes are widely applied in the detection of metal cations, an-
small molecules, and biomarkers with high sensitivity and selectivity [40–42].
ions, nitro-aromatic compounds, antibiotics, pesticides, volatile organic compounds, bio-
In this review, crystalline luminescent lanthanide–organic complexes with controllable
logical small molecules, and biomarkers with high sensitivity and selectivity [40–42].
structural features and excellent optical properties are discussed as zero-dimensional
In this review,
(0D) discrete crystalline
structures, luminescent
one-dimensional (1D)lanthanide–organic
and two-dimensional complexes with controlla-
(2D) coordination
ble structural features and excellent optical properties are discussed
polymers, and three-dimensional (3D) frameworks. Many studies have reported that some as zero-dimensional
(0D) discrete structures,
nitroaromatics, one-dimensional
such as nitrobenzene (1D) and two-dimensional
(NB), nitrophenol (2D) coordination
(2-NP or 4-NP), trinitrophenol
polymers,
(TNP), etc., and
can bethree-dimensional
detected by crystalline (3D) frameworks. Many studies
lanthanide–organic complex-based have reported
sensors. that
some nitroaromatics,
These explorations have suchledastonitrobenzene
the discovery(NB), nitrophenol
of sensing (2-NP
materials withorbetter
4-NP), trinitrophe-
detection
nol (TNP), etc.,
performance. can be detected
Moreover, by crystalline
various fluorescence lanthanide–organic
detection mechanisms ofcomplex-based
lanthanide–organic sensors.
 These explorations have led to the discovery of sensing materials with better detection
performance. Moreover, various fluorescence detection mechanisms of lanthanide–or-
Molecules 2023, 28, 4481 4 of 21
ganic complexes for nitroaromatics are summarized and sorted out to help other research-
ers better understand the fluorescence-detection mechanism of nitroaromatics and pro-
vide a theory for the rational design of new crystalline lanthanide–organic complex-based
complexes for nitroaromatics are summarized and sorted out to help other researchers
sensors.
better understand the fluorescence-detection mechanism of nitroaromatics and provide a
theory for the rational design of new crystalline lanthanide–organic complex-based sensors.
2. Fluorescent Sensing of Nitrobenzene Pollutants Based on the Structural
Characteristics
2. Fluorescent of Ln–Organic
Sensing Complexes
of Nitrobenzene Pollutants Based on the Structural
Characteristics of Ln–Organic Complexes
2.1. 0D Discrete Structure
2.1. 0D Discrete Structure
The
The discrete-structured lanthanidecomplexes
discrete-structured lanthanide complexes usually
usually possess
possess polynuclear
polynuclear metalmetal
sec- sec-
ondary
ondary building
buildingunits
units(SBUs)
(SBUs)andandthethe weak
weak intramolecular interactionsplay
intramolecular interactions playanan important
impor-
role in the sensing of nitro-based pollutants. The reported discrete
tant role in the sensing of nitro-based pollutants. The reported discrete lanthanide com-lanthanide complexes
include
plexesEu 2 [43],Eu
include Cd Nd4 Cd
2 8[43], [44],Yb
8 Nd4 18 [45], 18
[44],Yb Nd[45],
42 [46],
Nd42 and Yband
[46], 42 [47]
Yb42metal units,units,
[47] metal in which
in the
which the polynuclear
polynuclear metal clusters metal clusters
exhibit exhibit characteristic
characteristic nanoring nanoring structures
structures (Figure(Figure 2). et al.
2). Ma
Ma etprepared
[44,45] al. [44,45] Nd
prepared
4 and YbNd and Shi
, and
184 Yb18et, al.
and Shi et
[46,47] al. [46,47] Ln
synthesized synthesized
42 (Ln = Nd,Ln42La, Yb)
(Ln = Nd, La, Yb) nanowheel cluster structures. Due to their unique
nanowheel cluster structures. Due to their unique ring structures, special high-nuclearity ring structures,
special high-nuclearity lanthanide nanorings may show some advantages during the lumi-
lanthanide nanorings may show some advantages during the luminescent sensing, such
nescent sensing, such as a strong capture ability for analytes. A great deal of intramolecular
as interactions
a strong capture
existedability forlanthanide
in these analytes. A great dealsuch
complexes, of intramolecular
as hydrogen bonds interactions
or Ar-H–π existed
in interactions,
these lanthanide
which resulted in the formation of high-dimensional supramolecular struc-which
complexes, such as hydrogen bonds or Ar-H–π interactions,
resulted
tures orinthree-dimensional
the formation ofchannel
high-dimensional
structures, which supramolecular
are conducivestructures or three-dimen-
to the interaction with
sional channel
analytes structures, which are conducive to the interaction with analytes [44–47].
[44–47].

Figure
Figure2. 2.The
Thehigh-nuclearity
high-nuclearity lanthanide nanorings.(a)
lanthanide nanorings. (a)Cd
Cd 8Nd4 (Cd: green, Nd: blue, O: red, C:
8 Nd4 (Cd: green, Nd: blue, O: red,
gray). Adapted with permission from Ref. [44], 2021, American
C: gray). Adapted with permission from Ref. [44], 2021, American Chemical Society.
Chemical (b) Yb
Society. (Yb:
(b)18Yb18
blue,
O: (Yb:
red,blue,
C: gray).
O: red, C: gray). Adapted with permission from Ref. [45], 2022, Elsevier. (c) Yb42 (Yb: blue, red,
Adapted with permission from Ref. [45], 2022, Elsevier. (c) Yb 42 (Yb: blue, O:
C: O:
gray). Adapted with permission
red, C: gray). Adapted from Ref.
with permission from[47],
Ref. 2019, The The
[47], 2019, Royal Society
Royal of of
Society Chemistry.
Chemistry.

Discrete heterometallic
Discrete heterometallic d–f luminescent
d–f luminescentcomplexes are rarely
complexes aresynthesized due to harsh
rarely synthesized due to
synthetic conditions. For instance, a series of Zn–Ln frameworks consisted
harsh synthetic conditions. For instance, a series of Zn–Ln frameworks consisted of a longof a long Schiff
base ligand with a naphthyl backbone and two short polydentate ligands, in which the
Schiff base ligand with a naphthyl backbone and two short polydentate ligands, in which
Zn–Sm complex showed visible and NIR luminescent sensing of nitro explosives and
the Zn–Sm complex showed visible and NIR luminescent sensing of nitro explosives and
exhibited high sensitivity to 1,4-dinitrobenzene (1,4-DNB) and 2,4,6-trinitrotoluene (TNT)
exhibited
at the ppbhigh sensitivity
level [48]. to 1,4-dinitrobenzene (1,4-DNB) and 2,4,6-trinitrotoluene (TNT)
at the ppb level [48].
Investigations found that the discrete lanthanide complexes exhibited a strong lanthanide-
characteristic visiblefound
Investigations that the discrete
or near-infrared lanthanide complexes
(NIR) luminescent-sensing behavior exhibited a strong lan-
for nitro contami-
thanide-characteristic
nants with low detection visible
limitsor
innear-infrared (NIR)orluminescent-sensing
an aqueous solution behavior for ni-
acetonitrile, such as nitrobenzene
tro(NB), nitrophenolwith
contaminants (2-NPlowor detection
4-NP) and limits
2,4,6-trinitrophenol
in an aqueous (TNP). The selective
solution detection
or acetonitrile, such as
of certain nitro contaminants can be attributed to several factors, such as
nitrobenzene (NB), nitrophenol (2-NP or 4-NP) and 2,4,6-trinitrophenol (TNP). The selec- the size of the
channel
tive of the
detection of Ln complexes
certain or analyte molecules,
nitro contaminants and amounttoofseveral
can be attributed nitro compounds.
factors, suchIfas the
the volume of the measured object is appropriate to enter the cavity of the sensor, the
size of the channel of the Ln complexes or analyte molecules, and amount of nitro com-
fluorescence intensity may change and, thereby, exhibit a significant sensing effect.
pounds. If the volume of the measured object is appropriate to enter the cavity of the sen-
sor, the fluorescence intensity may change and, thereby, exhibit a significant sensing ef-
fect.
Molecules
Molecules2023,
2023,28,
28,x4481
FOR PEER REVIEW 5 5ofof22
21

2.2.
2.2.1D
1DLn-Coordination
Ln-CoordinationPolymersPolymers
Several
Several 1D-fluorescent lanthanide–organic
1D-fluorescent lanthanide–organic complexescomplexes for for sensing
sensing nitro
nitro pollutants
pollutants
were
were reported,
reported, possibly
possibly due due toto their
their monotonous
monotonous structural
structural characteristics
characteristicsand andindistinct
indistinct
fluorescent
fluorescent sensing
sensing performance.
performance. One-dimensional
One-dimensional Ln–organic
Ln–organic coordination
coordination polymers
polymers
[Ln(BDPO)(H
[Ln(BDPO)(H2O) 4]4 ]
2 O) (Ln(Ln==Eu Eufor
forCUST-623,
CUST-623,Tb TbforforCUST-624)
CUST-624)can canbebeprepared
preparedusing
using thethe
reaction
reaction ofof EuEuororTb Tb ionsions
withwith
the N,Nthe0 -bis(3,5-dicarboxyphenyl)-oxalamide
N,N′-bis(3,5-dicarboxyphenyl)-oxalamide ligand
ligand (BDPO).
[Ln(BDPO)(H
(BDPO). 2 O)4 ] has2O)
[Ln(BDPO)(H a 1D framework
4] has structure structure
a 1D framework with two kinds
with twoof 1Dkinds
openof channels
1D open in
the b-axis direction. Such 1D Ln–organic complexes can be used
channels in the b-axis direction. Such 1D Ln–organic complexes can be used as a fluores- as a fluorescent sensor
to detect
cent sensor TNPto with
detectthe TNPlowwith
detection
the low limit of 0.21 µM
detection limit[49]. Further,
of 0.21 μM 1D [Eu(L)
[49]. 6 (DMF)]
Further, 1D
(L = 2-(2-formylphenoxy)
[Eu(L) acetic acid) canacetic
6(DMF)] (L= 2-(2-formylphenoxy) be packed
acid)into
canabe2Dpacked
structureintothrough
a 2D hydrogen
structure
bonding,hydrogen
through and it hasbonding,
a good selectivity
and it has as awell as aselectivity
good high sensitivity
as welltoasTNP withsensitivity
a high the detectionto
limitwith
TNP of rapid responselimit
the detection of 3.39 µM inresponse
of rapid a CH3 CN solution
of 3.39 μM in (Figure
a CH3CN 3). The good(Figure
solution detection3).
ability
The goodtowards TNPability
detection over other nitroTNP
towards explosives may be
over other ascribed
nitro to themay
explosives possible quenching
be ascribed to
mechanism of competitive absorption, photoinduced electron
the possible quenching mechanism of competitive absorption, photoinduced electron transfer and hydrogen-bond
interaction
transfer and[50]. In addition, interaction
hydrogen-bond the mixed ligands
[50]. In are used tothe
addition, construct the 1D are
mixed ligands Ln–organic-
used to
coordination
construct the 1Dpolymers, which is regardedpolymers,
Ln–organic-coordination as a goodwhich
strategy. For instance,
is regarded the reaction
as a good strategy. of
Eu(III)
For ion with
instance, themixed
reaction ligands of 2,3,4,5-tetrafluorobenzoic
of Eu(III) ion with mixed ligandsacid and 1,10-phenanthroline
of 2,3,4,5-tetrafluorobenzoic
afforded
acid and a1,10-phenanthroline
1D structural tetranuclear afforded[Eua4 ]1Dcomplex with tetranuclear
structural two crystallographically
[Eu4] complex indepen-
with
dent Eu 3+ ions, which exhibited a highly sensitive response toward nitrobenzene at the
two crystallographically independent Eu ions, which exhibited a highly sensitive re-
3+
ppm concentration
sponse toward nitrobenzene[51]. at the ppm concentration [51].

Schematic
Figure 3.3.Schematic
Figure illustration
illustration of 1Dof 1D Eu–organic
Eu–organic complexcomplex [Eu(L)n 6(HL
[Eu(L)6(DMF)] (DMF)] n (HL = 2-(2-
= 2-(2-formylphe-
noxy)acetic acid) havingacid)
formylphenoxy)acetic high selectivity
having high and selectivity
sensitivity to TNP
and in acetonitrile.
sensitivity to TNP (a) Concentration-
in acetonitrile.
dependent fluorescence quenching efficiencies of [Eu(L) (DMF)] suspension
(a) Concentration-dependent fluorescence quenching efficiencies of [Eu(L)6 (DMF)]
6 n based onn the 618 nm
suspension
peak. Gradually addition of TNP solution to the [Eu(L) 6(DMF)]n suspension (from 0 to 200 lL, kex =
based on the 618 nm peak. Gradually addition of TNP solution to the [Eu(L)6 (DMF)]n suspension
350
(fromnm);
0 to(b)
200The luminescence
lL, kex quenching
= 350 nm); (b) efficiencies
The luminescence of different
quenching Nitro explosives
efficiencies of differenttowards the
Nitro explo-
CH3CN dispersion of [Eu(L)6(DMF)]n. Adapted with permission from Ref. [50], 2022, Elsevier.
sives towards the CH3CN dispersion of [Eu(L)6 (DMF)]n . Adapted with permission from Ref. [50],
2022, Elsevier.
These 1D lanthanide complexes can be used as luminescence sensors to detect NB or
TPA in an aqueous
These or CHcomplexes
1D lanthanide 3CN solution with the low detection limits at the μM level
can be used as luminescence sensors to detect NB
through
or TPA in an aqueous or CHluminescence
the alteration in its CN solution property, exhibiting
with the low thelimits
detection characteristic
at the µMvisible
level
3
luminescence of Eu or Tb ions. The fluorescence-detection mechanism of nitro contami-
through the alteration in its luminescence property, exhibiting the characteristic visible
nants involves of
luminescence photoinduced
Eu or Tb ions.electron transfer (PET), resonance
The fluorescence-detection energyoftransfer
mechanism (RET),
nitro contami-
competitive absorption of excitation energy (CA), and weak interactions. Moreover,
nants involves photoinduced electron transfer (PET), resonance energy transfer (RET), a
large number of hydrogen bonds in the 1D chain structure and weak interactions
competitive absorption of excitation energy (CA), and weak interactions. Moreover, between
complexes and analytes
a large number playbonds
of hydrogen an important
in the 1Drole in structure
chain the sensing
andprocess.
weak interactions between
complexes and analytes play an important role in the sensing process.
Molecules 2023, 28, x FOR PEER REVIEW 6 of 22

Molecules 2023, 28, 4481 6 of 21

2.3. 2D Ln-Coordination Polymers
Chemists explored a few 2D fluorescent lanthanide-based homometallic (f-f group)
or 2.3.
heterometallic (d–f group)
2D Ln-Coordination Polymers organic complexes as sensing materials for the detection of
nitroaromatics.
Chemists The studies
explored a fewrevealed that thelanthanide-based
2D fluorescent structural characteristics
homometallic and (f-f
thegroup)
presence of
weak interactions between 2D sheets (hydrogen bond, X…X bond, π
or heterometallic (d–f group) organic complexes as sensing materials for the detection of stacking interaction)
arenitroaromatics.
beneficial to the Theinteraction
studies revealedof the analyte
that with material
the structural and theand
characteristics fluorescence
the presenceresponse
of
of weak
the luminescent species 2D
interactions between [52–57].
sheets (hydrogen bond, X . . . X bond, π stacking interaction)
areLiu
beneficial to the interaction
et al. reported a new of 2DtheDy-organic
analyte withcomplex
material [Dy(L)(NO
and the fluorescence
3)(DMF)3response
]n (H2L = 2,5-
of the luminescent species [52–57].
di(1H-1,2,4-triazol-1-yl) terephthalic acid, DMF = N, N-dimethylformamide)} with binu-
Liu et al. reported a new 2D Dy-organic complex [Dy(L)(NO3 )(DMF)3 ]n (H2 L = 2,5-
clear units as a ratiometric luminescent sensor for nitro compounds (such as 4-NP) in
di(1H-1,2,4-triazol-1-yl) terephthalic acid, DMF = N, N-dimethylformamide)} with binu-
aqueous solutions; the lowest detection limit (0.0676 μM) indicates a high sensitivity [52].
clear units as a ratiometric luminescent sensor for nitro compounds (such as 4-NP) in aque-
Theousluminescence
solutions; the response of another
lowest detection limit 2D complex,
(0.0676 [Eu(TFTA)
µM) indicates 1.5(H2O)2]·H2O (TFTA = tet-
a high sensitivity [52]. The
rafluoroterephthalate),
luminescence response of another 2D complex, [Eu(TFTA)1.5 (H2 O)2 ]·H2 O and
in methanol was influenced by the primary (TFTA secondary
= tetraflu- inner
filter effects (IFE) of in
oroterephthalate), nitroaromatic
methanol was compounds
influenced by (4-NTP, 2,4-DNP
the primary andand TNP). The
secondary innermodelling
fil-
andtercorrection
effects (IFE)ofofIFE revealed the
nitroaromatic mechanism
compounds of 2,4-DNP
(4-NTP, static and anddynamic
TNP). The quenching
modellingin the
and correction
complex, and F–Fofinteractions
IFE revealedwere the mechanism
also involved of static
in theand dynamic
assembly ofquenching
2D structures in the
into 3D
complex, and F–F
supramolecular interactions
entities; were also
as predicted, involved
these in the assembly
interactions weaken of 2D the
with structures into con-
lanthanide
3D supramolecular
traction [53]. The similarentities;
Br–Bras predicted,
interactions these interactions
were found inweaken
a serieswith
of 2Dthelanthanide
lanthanide coor-
contraction [53]. The similar Br–Br interactions were found in a series of 2D lanthanide co-
dination polymers {Eu2(TBrTA)3(H2O)8·2H2O}n (TBrTA = tetrabromoterephthalate), the
ordination polymers {Eu2 (TBrTA)3 (H2 O)8 ·2H2 O}n (TBrTA = tetrabromoterephthalate), the
quenching
quenchingrate rate of nitroaromatic
of nitroaromatic compounds
compounds waswas
85%,85%, including
including 4-nitrophenol,
4-nitrophenol, dinitrophe- dinitro-
phenol, and trinitrophenol (picric acid), with the main quenching mechanisms
nol, and trinitrophenol (picric acid), with the main quenching mechanisms of competitive of compet-
itive absorption,
absorption, photoinduced
photoinduced electronelectron transfer,
transfer, and theand the electrostatic
electrostatic process
process [54] (Figure[54]
4). (Figure
4).

Figure
Figure 4.4.Scheme
Scheme
of designofand design and
detection for detection
nitroaromatic for of
compounds nitroaromatic
{Eu2 (TBrTA)3 (H2compounds
O)8 ·2H2 O}n of
{Eucoordination
2(TBrTA)3(H 2 O) 8 ·2H2 O} n coordination polymer based on tetrabromoterephthalic acid.
polymer based on tetrabromoterephthalic acid. Adapted with permission from Ref. [54], Adapted
with permission
2018, American from
ChemicalRef.Society.
[54], 2018, American Chemical Society.

Lanthanide coordination
Lanthanide coordination polymers
polymersconstructed from from
constructed mixedmixed
organicorganic
ligands exhibit
ligandsrich
exhibit
structural features and good luminescent sensing properties for nitroarmoatics.
rich structural features and good luminescent sensing properties for nitroarmoatics. How- However,
lanthanide
ever, ions are
lanthanide ionsnot
areeasy
nottoeasy
coordinate with nitrogen
to coordinate with atoms,
nitrogen andatoms,
it is difficult
and ittoisobtain
difficult to
mixed-ligand products by adding nitrogen-containing auxiliary ligands. It is through
obtain mixed-ligand products by adding nitrogen-containing auxiliary ligands. It is
through luck our group prepared a series of 2D lanthanide coordination polymers with a
mixed ligand of 2/5-(pyridine-2-ylmethoxy) isophthalic acid and nitrogen-containing
 Molecules 2023, 28, 4481 7 of 21
Molecules 2023, 28, x FOR PEER REVIEW 7 of 2

luck our group prepared a series of 2D lanthanide coordination polymers with a mixed
ligand of 2/5-(pyridine-2-ylmethoxy)
auxiliary ligands, which have highisophthalic
selectivityacid
andand nitrogen-containing
sensitivity auxiliary
for the detection of TNP a
ligands,
nM level (Figure 5) [55]. Obviously, the addition of a nitrogen-containing nM
which have high selectivity and sensitivity for the detection of TNP at levelis condu
ligand
(Figure 5) [55]. Obviously, the addition of a nitrogen-containing ligand is conducive
cive to the formation of non-covalent bonds and the promotion of the fluorescence sensing
to the formation of non-covalent bonds and the promotion of the fluorescence sensing
of nitrocompounds.
of nitrocompounds.

Figure5.5. (a)
Figure (a) The
The coordination
coordinationenvironment
environment of of
2D2DTb–organic
Tb–organiccomplex
complexbased on mixed
based ligands
on mixed ligands (Tb
(Tb:
light blue, N: dark blue, O: red, C: gray); (b) 2D network; (c) the fluorescence intensityatat 549 nm
light blue, N: dark blue, O: red, C: gray); (b) 2D network; (c) the fluorescence intensity
549
upon nmadding
upon adding different
different nitro explosives
nitro explosives (λexnm);
(λex = 313 = 313
(d)nm); (d) changes
changes in the fluorescence
in the fluorescence spectrum upon
spectrum upon gradually adding TNP. Adapted with permission from
gradually adding TNP. Adapted with permission from Ref. [55], 2022, Elsevier. Ref. [55], 2022, Elsevier.

Although the preparation of 2D lanthanide-based heterometallic coordination poly-

mers Although the preparation
is a great challenge, a few of 2D lanthanide-based
complexes heterometallic
have been reported and showed coordination
fluores- poly
merssensing
cent is a great challenge,
properties a few
for nitro complexes For
contaminants. have been reported
example, and showedcom-
f–f mixed-lanthanide fluorescen
sensing
plexes properties
with differentfor nitroratios
mixed contaminants.
display a 2D For example,
sheet-like f–f mixed-lanthanide
structure. Owing to the hy- complexes
with different
drogen mixed ratios
bond interactions, thedisplay a 2D sheet-like
2D structures are easily structure.
packed into Owing to the hydrogen
3D frameworks and bond
exhibit a goodthe
interactions, sensing performance
2D structures for 4-NP,
are easily such into
packed as 1-Eu
3D 0.5 Tb0.5 [56]. In
frameworks addition,
and exhibit a good
2D d-f-block
sensing Cd(II)-lanthanide(III)
performance for 4-NP, such heterometallic-organic
as 1-Eu0.5Tb0.5 [56].frameworks [CdCl(L)Eu
In addition, x Tby - Cd(II)
2D d-f-block
(H 2 O)(DMA)](NO
lanthanide(III) 3 ) · 3DMA (IFMC-36-Eu x
heterometallic-organicTby ) showed characteristic
frameworks sharp emission bands
[CdCl(L)EuxTby
of Eu(III) and Tb(III), and the intensities of red and green were tuned through changing
(H2O)(DMA)](NO3)·3DMA (IFMC-36-EuxTby) showed characteristic sharp emission bands
the ratios of Eu(III) and Tb(III). It is worth noting that the luminescence property of IFMC-
of Eu(III)
36-Eu and aTb(III),
suggests potential andapplication
the intensities
in theof red andofgreen
detection were tuned through
the small-molecule pollutantchanging
the ratios of via
nitrobenzene Eu(III) and Tb(III).
significant It is worth
fluorescence noting[57].
quenching that the luminescence property of IFMC
36-Eu suggests a potential application in the detection of the small-molecule pollutant ni
2.4. 3D Ln–Organic
trobenzene Frameworks
via significant fluorescence quenching [57].
Due to the high coordination number of lanthanide ions and their strong coordination
ability
2.4. 3Dwith the oxygen
Ln–Organic atoms of the carboxylate ligand, the fluorescent lanthanide–organic
Frameworks
framework with a 3D structure accounts for a large proportion of research. Owing to the
Due to the high coordination number of lanthanide ions and their strong coordina
advantages of the 3D microporous structure, the fluorescence-sensing performance of 3D
tion ability with the
lanthanide–organic oxygen atoms
frameworks of better
is much the carboxylate ligand,
than those of 0D, 1Dtheandfluorescent lanthanide–
2D lanthanide–
organic complexes; therefore, 3D lanthanide–organic frameworks are used not only for the Owing
organic framework with a 3D structure accounts for a large proportion of research.
to the advantages
detection of the p-nitroaniline
of nitrobenzene, 3D microporous structure, thebut
and 4-nitophenol, fluorescence-sensing performance
also for 3,4-dinitrotoluene
of 3D
and lanthanide–organic frameworks is much better than those of 0D, 1D and 2D lantha
2,4,6-trinitrophenol.
nide–organic complexes; therefore, 3D lanthanide–organic frameworks are used not only
for the detection of nitrobenzene, p-nitroaniline and 4-nitophenol, but also for 3,4-dinitro
toluene and 2,4,6-trinitrophenol.
The hydrothermal reaction of lanthanide ions (Ln3+) and 2,5-di(1H-1,2,4-triazol-1
 Molecules 2023, 28, 4481 8 of 21
Molecules 2023, 28, x FOR PEER REVIEW

The hydrothermal reaction of lanthanide ions (Ln3+ ) and 2,5-di(1H- 1,2,4-triazol-1-

yl)terephthalic
{[Ln(dttpa)1.5acid(H2(H 2 dttpa) formed
O)]·0.75H 2O}n lanthanide
(Ln = Tb3+metal
, Er3+coordination polymers
) [58], in which {[Ln(dttpa)
Eu–CP effectively
1.5 se
(H2O)2]·H2O}n (Ln–CP, Ln = La3+3+ , Ce3+, Nd3+, Sm3+, Eu3+) and {[Ln(dttpa)1.5(H3+2O)]·0.75H2O}n
the visible emission of Tb and shows high selectivity for Tb and stable and hig
(Ln = Tb3+ , Er3+ ) [58], in which Eu–CP effectively sensitizes the visible emission of Tb3+
tiveshows
and response with a minimal
high selectivity for Tb3+ and detection
stable andlimit
highof 0.00988
sensitive μM; furthermore,
response with a minimalTb-CP
good luminescence
detection limit of 0.00988sensor to detect nitrobenzene
µM; furthermore, Tb-CP acts as a(NB)
good with a detection
luminescence sensorlimit
to of 0.0
Moreover,
detect the fluorescence
nitrobenzene quenching
(NB) with a detection limit of Tb-CPµM.
of 0.0125 forMoreover,
NB can the
be attributed
fluorescenceto the c
quenching
tive absorption mechanism and the photo-induced electronic transfer and
of Tb-CP for NB can be attributed to the competitive absorption mechanism mechanism
the photo-induced electronic transfer mechanism of the excited-state interaction between
excited-state interaction between the luminescent material and NB (Figure 6).
the luminescent material and NB (Figure 6).

Figure 6. (a) Two-dimensional structure of {[Tb(dttpa)1.5 (H2 O)]·xH2 O}n (Tb–CP); (b) luminescence
Figure 6. (a) Two-dimensional structure of {[Tb(dttpa)1.5(H2O)]·xH2O}n (Tb‒CP); (b) lumi
intensities of the 5 D4 → 7 F5 transition (542 nm) for Tb–CP CH3 CN suspension with additional various
intensities of the 5D4 → 7F5 transition (542 nm) for Tb‒CP CH3CN suspension with additiona
solvents (0.1 mM) (λex = 248 nm); (c) sensing for NB of Tb–CP; (d) curve plotting the luminescence
solventsand
intensity (0.1 mM) (λex of
concentration = 248 nm); Stern–Volmer
NB (inset: (c) sensing for
plotsNB of linear
of the Tb‒CP; part(d) curve
of the plotting
curve to obtainthe lumi
intensity and concentration of NB (inset: Stern–Volmer plots of
Ksv). Adapted with permission from Ref. [58], 2022, The Royal Society of Chemistry.the linear part of the curve
Ksv). Adapted with permission from Ref. [58], 2022, The Royal Society of Chemistry.
In general, most studies were focused on Eu/Tb complexes for their excellent lumines-
cence properties, but a few other Ln–organic complexes were also explored and applied
In general, most studies were focused on Eu/Tb complexes for their excelle
to fluorescent sensors for the detection of nitroaromatic compounds. For example, the
nescence properties,
solvothermal but a3 )few
reaction of La(NO other Ln–organic complexes were also explored
3 ·6H2 O, tetrakis(4-carboxyphenyl)ethylene (TCPE) and
plied toyielded
L-proline fluorescent
the Lasensors for the
metal–organic detection
framework of nitroaromatic
La(HTCPE)(H compounds.
2 O)2 , which could be For e
employed as a sensitive and selective fluorescence sensor for nitro-containing
the solvothermal reaction of La(NO3)3·6H2O, tetrakis(4-carboxyphenyl)ethylene aromatic
compounds,
and L-prolinesuch as p-nitroaniline
yielded the La(NA). When NA wasframework
metal–organic added into the suspension system
La(HTCPE)(H 2O)2, whic
of La(HTCPE)(H2 O)2 , fluorescence was almost completely quenched [59]. Due to the harsh
be employed as a sensitive and selective fluorescence sensor for nitro-containing a
synthesis conditions, 3D luminescent d-f block-based heterometallic organic complexes
compounds,
have rarely beensuch as p-nitroaniline
synthesized; these deserve (NA). When
further NA was
exploration in added into
the future the suspension
to broaden
of La(HTCPE)(H
the 2O)2, fluorescence
family of 3D luminescent was almost completely quenched [59]. Due to th
Ln–organic complexes.
synthesis conditions, 3D luminescent d-f block-based heterometallic organic co
3. Detection Effect of Ln–Organic Complexes on Different Nitro Pollutants
have rarely been synthesized; these deserve further exploration in the future to
Nitro pollutants are closely related to production and daily life due to their wide use
the
in family of
industrial 3D luminescent
processes, such as for Ln–organic complexes. and dyes. It is of great
pesticides, pharmaceuticals
significance to develop low-cost and effective fluorescence probe material for the detection
3.low-concentration
of Detection Effect of Ln–Organic
hazardous Complexes
nitro pollutants onselectivity
with high Different andNitro Pollutants
sensitivity.
Nitro pollutants are closely related to production and daily life due to their w
in industrial processes, such as for pesticides, pharmaceuticals and dyes. It is of g
nificance to develop low-cost and effective fluorescence probe material for the d
Molecules 2023, 28, 4481 9 of 21

3.1. Nitrobenzene (NB)

Nitrobenzene (NB), as the simplest nitroaromatic compound, is widely used in the
synthesis of many products in industry, and leads to air, water, and soil pollution, as
Molecules 2023, 28, x FOR PEER REVIEW 9 of 22
well as serious safety problems. Moreover, since NB is highly toxic, difficult to degrade,
carcinogenic, and easy to settle, once it is exposed to groundwater and soil, it will have
adverse effects on human health and the environment. The rapid and sensitive detection of
adverse effects on human health and the environment. The rapid and sensitive detection
NB is a crucial task; thus, many approaches have been developed for NB detection, such as
of NB is a crucial task; thus, many approaches have been developed for NB detection, such
chromatography, spectrophotometry, electrochemical method, and so on [37]. However,
as chromatography, spectrophotometry, electrochemical method, and so on [37]. How-
these
ever, methods
these methods are
arecomplex,
complex,expensive, andtime-consuming.
expensive, and time-consuming. ManyMany lanthanide
lanthanide com- complexes
can be used as fluorescence materials to detect NB through the
plexes can be used as fluorescence materials to detect NB through the alteration in fluo-alteration in fluorescence
properties
rescence and, usually,
properties show
and, usually, high
show sensitivity
high sensitivityand
and selectivity,
selectivity, due duetotoNB NB inducing fluo-
induc-
rescence
ing quenching
fluorescence quenchingof lanthanide complexes
of lanthanide complexes in invarious
variousorganic
organicsolvents.
solvents. As As shown in
Figurein7, aFigure
shown 3D Eu–organic
7, a 3D complex {[Eucomplex
Eu–organic 2 (NSBPDC) {[Eu 32(H O)
(NSBPDC)
2 4 ] · 7(H
3 (H22 O)}
O) 4 (H
]·7(H
n 2 NSBPDC
O)}
2 n = 6-
(Hnitro-2,2
2NSBPDC
0 -sulfone-4,4 0 -dicarboxylic acid), as a fast
= 6-nitro-2,2′-sulfone-4,4′-dicarboxylic acid),and
as arecyclable
fast and recyclable
fluorescence fluores-sensor, exhib-
cence
ited sensor, exhibited good
good fluorescence fluorescence
sensing on NBsensing on NB via
via a turn-off a turn-off
response with response with a
a low detection limit of
low detection
11.315 µM [60]. limit of 11.315 μM [60].

Figure 7. (a) Coordination environment of EuIII ions in {[Eu2III (NSBPDC)3(H2O)4]·7(H2O)}n (Eu: green,
Figure 7. (a) Coordination environment of Eu ions in {[Eu2 (NSBPDC)3 (H2 O)4 ]·7(H2 O)}n
N: blue, O: red, C: gray); (b) the 3D structure of {[Eu2(NSBPDC)3(H2O)4]·7(H2O)} n with 1D channels
(Eu:the
along green,
a axisN: blue,
(Eu: green,O:N:
red, C: O:
blue, gray); (b)gray);
red, C: the 3D structure
(c) the of {[Euintensity
luminescence 2 (NSBPDC) 3 (H
at 614 nm of4 ]·7(H2 O)}n
2 O)
with
{[Eu 1D channels
2(NSBPDC) 3(H2O)4along then dispersed
]·7(H2O)} a axis (Eu:in green,
variousN: blue, (λ
solvents O:ex red,
= 359C: gray);
nm); (c) luminescence
and (d) the luminescence inten-
intensity
sity at of
614{[Eu
nm 2(NSBPDC) 3(H2O)4]·7(H2(H
of {[Eu2 (NSBPDC) 3 O)}2nO)
upon gradual
4 ]·7(H 2 O)}naddition
dispersed of NB. Adaptedsolvents
in various with permis-
(λex = 359 nm);
sion from Ref. [60], 2019, Elsevier.
and (d) luminescence intensity of {[Eu2 (NSBPDC)3 (H2 O)4 ]·7(H2 O)}n upon gradual addition of NB.
Adapted with permission from Ref. [60], 2019, Elsevier.
However, there are few in-depth studies on the fluorescence quenching mechanism
of lanthanide–organic complexes induced by adding NB. To investigate the mechanism
However, there are few in-depth studies on the fluorescence quenching mechanism
of fluorescence quenching with NB, Liu et al. designed and prepared a Tb–FDA complex,
of lanthanide–organic complexes induced by adding NB. To investigate the mechanism
{[Tb(FDA)1.5(DMF)]⋅DMF}n, using the reaction of Tb3+ and 2,5-furandicarboxylic acid
(Hof fluorescence quenching with NB, Liu et al. designed and prepared a Tb–FDA complex,
2FDA) under solvothermal conditions, and used it as a highly selective and sensitive
{[Tb(FDA) ·DMF}n , using 3+ and 2,5-furandicarboxylic acid
fluorescent 1.5 (DMF)]
probe for nitrobenzene and Fethe
3+. Thereaction of Tbquenching
fluorescence mechanism was
(H2 FDA)
explained byunder solvothermal
the lowest unoccupiedconditions, and (LUMO)
molecular orbital used it as a highly
energy level selective and sensitive
of NB (−2.437
fluorescent
eV), probethan
which is lower forthat
nitrobenzene
of the H2FDA and Fe3+(−1.954
ligand . The fluorescence quenching
eV) [61]. Hidalgo-Rosa mechanism
et al.
was explained
further expanded theby knowledge
the lowestofunoccupied molecular
the selective-sensing orbital (LUMO)
mechanism energy level of NB
of nitro compounds
using luminescent terbium metal–organic frameworks [Tb(BTTA)1.5(H2O)4.5]n (H2BTTA =
Molecules 2023, 28, 4481 10 of 21

(−2.437 eV), which is lower than that of the H2 FDA ligand (−1.954 eV) [61]. Hidalgo-
Rosa et al. further expanded the knowledge of the selective-sensing mechanism of nitro
Molecules 2023, 28, x FOR PEER REVIEW 10 of 22
compounds using luminescent terbium metal–organic frameworks [Tb(BTTA)1.5 (H2 O)4.5 ]n
(H2 BTTA = 2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acid) through multiconfigurational
ab-initio calculations [62].
2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acid) through multiconfigurational ab-initio cal-
culations
3.2. Nitrophenol (4-NP[62].
or 2-NP)
Nitrophenol (4-NP or(4-NP
3.2. Nitrophenol 2-NP)oris2-NP)
one of the smaller nitroaromatics with one electron-
withdrawing nitro group and one electron-donating hydroxyl group on a benzene ring. It
Nitrophenol (4-NP or 2-NP) is one of the smaller nitroaromatics with one electron-
is mainly used as intermediate of pesticides, medicines,
withdrawing nitro group and one electron-donating dyes and othergroup
hydroxyl fine chemicals,
on a benzene and,
ring. It
therefore, causes serious pollution due to its high toxicity. The highly sensitive
is mainly used as intermediate of pesticides, medicines, dyes and other fine chemicals, detection
of NP in water and,istherefore,
very important for water
causes serious environment
pollution due to its protection,
high toxicity.human health
The highly and de-
sensitive
ecological environment
tection of NP in water is very important for water environment protection, human of
safety. GC, AAS, MS, etc., are usually used for the detection health
NP, but someand potential
ecological disadvantages limit their
environment safety. applications
GC, AAS, [56].
MS, etc., are Therefore,
usually the
used for theuse of
detection
of NP,
efficient sensors for but some potential
detecting disadvantages
NP is extremely limit their
convenient andapplications
significant;[56]. Therefore, the
in particular, the use
of efficient sensors for detecting NP is extremely convenient
development of Ln–organic complex-based fluorescence sensors with high sensitivity for and significant; in particular,
the development
NP is of pivotal of Ln–organic complex-based fluorescence sensors with high sensitivity
practical significance.
for NP is of pivotal
Lin et al. designed and prepared practicala significance.
series of {[Ln(HL)]·3DMF·3H2 O}n (Ln = Eu and Tb,
Lin et al. designed and prepared a series of {[Ln(HL)]·3DMF·3H2O}n (Ln = Eu and Tb,
H4 L = 1,4-bis(2 ,2 ,6 ,6 -tetracarboxy-1,40 :4,400 -pyridyl)benzene) (LZG-Eu and LZG-Tb)-
0 00 0 00
H4L = 1,4-bis(2′,2″,6′,6″-tetracarboxy-1,4′:4,4″-pyridyl)benzene) (LZG-Eu and LZG-Tb)-
based sensors to sense 4-NP with a detection limit of 0.0112 µM in deionized water, showing
based sensors to sense 4-NP with a detection limit of 0.0112 μM in deionized water, show-
a promising Ln–organic
ing a promising complex sensor
Ln–organic for 4-NP
complex detection
sensor in detection
for 4-NP actual water compared
in actual with
water compared
those reported Lnthose
with complexes
reported(Figure 8) [63]. (Figure 8) [63].
Ln complexes

Figure 8. (a) The 3D molecular

Figure 8. (a)The 3Dstructure
molecular ofstructure
{[Tb(HL)]of·3DMF ·3H2 O}n (LZG-Tb)
{[Tb(HL)]·3DMF·3H showing
2O}n (LZG-Tb) the Tbthe
showing 4 C3Tb
O64C3O6
subunit
subunit and chair and chair conformational
conformational hexagon cavityhexagon cavityalong
viewing viewing along
c-axis c-axis(color
(color modes:modes:
green,green, Tb; red,
Tb; red,
O; blue, N; gray, C); (b) the luminescence response of {[Eu(HL)]·3DMF·3H2O}n (LZG-Eu) to different
O; blue, N; gray, C); (b) the luminescence response of {[Eu(HL)]·3DMF·3H2 O}n (LZG-Eu) to different
concentrations of 4-NP (0–7.5 μM) in deionized water; (c) the luminescence response of LZG-Tb to
concentrationsdifferent
of 4-NPconcentrations
(0–7.5 µM) in of deionized water;
4-NP (0–1 μM) (c) the luminescence
in deionized water. Adaptedresponse of LZG-Tb
with permission from Ref.
to different concentrations of 4-NP
[63], 2021, The Royal (0–1ofµM)
Society in deionized water. Adapted with permission from
Chemistry.
Ref. [63], 2021, The Royal Society of Chemistry.
To detect 2-NP, a few Ln–organic-complex-based sensors were also designed and
To detect prepared.
2-NP, aFor fewexample, the large [Ln42L14(OH)28(OAc)
Ln–organic-complex-based 84] (Ln
sensors 42, Ln
were = Nd,
also Yb, HL =and
designed 3-meth-
oxysalicylaldehyde) coordination polymer nanorings-based
prepared. For example, the large [Ln42 L14 (OH)28 (OAc)84 ] (Ln42 , Ln = Nd, Yb, HL = 3- sensor exhibits NIR lumines-
cence sensing coordination
methoxysalicylaldehyde) for 2-NP in CH 3CN with the detection limit from 8.22 to 27.1 μM [46,47].
polymer nanorings-based sensor exhibits NIR lumi-
The existence of the electron-withdrawing
nescence sensing for 2-NP in CH CN with the detection grouplimit
on the benzene
from 8.22 toring likely
27.1 µMpromotes
[46,47]. the
3
Molecules 2023, 28, 4481 11 of 21

The
existence of the electron-withdrawing group on the benzene ring likely11promotes
Molecules 2023, 28, x FOR PEER REVIEW of 22 the
fluorescence quenching of lanthanide coordination polymers; thus, the sensing performance
of Ln-CPs, for NP, has been discovered in recent years.
fluorescence quenching of lanthanide coordination polymers; thus, the sensing perfor-
3.3.
mance2,4,6-Trinitrophenol
of Ln-CPs, for NP,(TNP)
has been discovered in recent years.
Picric acid (PA), or 2,4,6-Trinitrophenol (TNP), possesses three electron-withdrawing
3.3. 2,4,6-Trinitrophenol
nitro groups and one (TNP) electron-donating hydroxyl group on a benzene ring. As a common
and typicalacid
Picric (PA), or 2,4,6-Trinitrophenol
malignant organic pollutant, (TNP),
TNP ispossesses
used widelythree inelectron-withdrawing
industries for dyes, explo-
sives, pharmaceuticals, fireworks, firecrackers and leather. High ring.
nitro groups and one electron-donating hydroxyl group on a benzene As aand
toxicity, commonharmfulness
and typical malignant organic pollutant, TNP is used widely in
to eyes, skin and the respiratory system inspired many researchers to efficientlyindustries for dyes, explo-
detect TNP.
sives, pharmaceuticals, fireworks, firecrackers and leather. High toxicity, and harmfulness
The traditional detection methods, including HPLC, RS, IMS, GC, MS and MIT, could be
to eyes, skin and the respiratory system inspired many researchers to efficiently detect
used to detect explosives, such as TNP; some potential limitations of these technologies
TNP. The traditional detection methods, including HPLC, RS, IMS, GC, MS and MIT,
restrict their application [64]. TNP remains in a dissociated form in solution and can interact
could be used to detect explosives, such as TNP; some potential limitations of these tech-
with the restrict
nologies positive center
their on the [64].
application fluorophore
TNP remains dueintoaits low pKaform
dissociated valuein (pKa = 0.42)
solution and [35,65];
thus, the fluorescence
can interact sensing
with the positive method
center on theisfluorophore
suitable fordue theto detection
its low pKa of TNP
valuein solution.
(pKa =
0.42)The Ln–organic
[35,65]; complexes-based
thus, the fluorescence sensingsensors
method can effectively
is suitable for thedetect TNPofwith
detection TNP highin sensi-
tivity and selectivity in aqueous solution. Xu et al. prepared a 3D [Tb(TCBA)(H2 O)2 ]2 ·DMF
solution.
(H3 TCBA = tris(30 -carboxybiphenyl)amine;
The Ln–organic complexes-based sensors can DMF = dimethylformamide)
effectively detect TNP with high by sensi-
the solvother-
tivityreaction
mal and selectivity
of Tbin 3+ aqueous
with a solution. Xu et al.Hprepared
propeller-like TCBA a 3D [Tb(TCBA)(H
ligand. The 2O)2]2·DMF
resultant Tb–organic
3
(H3TCBAfeatures
complex = tris(3′-carboxybiphenyl)amine;
1D triangular channels. DMF Such = dimethylformamide)
a structure indicated by the
high solvother-
selectivity, with
malextremely
an reaction oflowTb3+detection
with a propeller-like
limit aboutH1.64
3TCBA ligand. The resultant Tb–organic com-
ppb implied a high sensitivity for TNP explo-
plex features 1D triangular channels.
sive [66]. The lowest detection limit means Such a structure indicated
the highest high selectivity,
sensitivity with an
of the sensor, compared
extremely low detection limit about 1.64 ppb implied a high sensitivity for TNP explosive
with the previously reported Ln-based sensors [39,44,45,49,50,53,55]. The strong host–guest
[66]. The lowest detection limit means the highest sensitivity of the sensor, compared with
interactions between the Tb metal–organic framework (Tb-MOF) and TNP are captured and
the previously reported Ln-based sensors [39,44,45,49,50,53,55]. The strong host–guest in-
accurately determined
teractions between the Tbby online microcalorimetry,
metal–organic framework (Tb-MOF) which and provides
TNP are a distinctive
captured and thermody-
namic perspective to understand the heterogeneous sensing behaviors.
accurately determined by online microcalorimetry, which provides a distinctive thermo- Another interesting
work
dynamic about sensing to
perspective TNP using anthe
understand Ln–organic
heterogeneous complex
sensingis that a proportional
behaviors. fluorescence
Another inter-
probe
esting RGH-Eu(BTC)
work about sensing for TNP recognition
TNP using was prepared
an Ln–organic complexby fixing
is that a rhodamine
a proportional derivative
fluo-
(RGH)
rescenceon the surface
probe RGH-Eu(BTC)of the for
luminescent Eu coordination
TNP recognition was preparedpolymerby fixingEu(BTC)
a rhodamine [67]. In the
derivativeof
presence (RGH)
TNP, on thetheredsurface of the luminescent
fluorescence emission of EuEu(BTC)
coordinationwas polymer
quenched Eu(BTC)
in the donor–
[67]. In the
acceptor presence
electron of TNP,process.
transfer the red fluorescence emission of Eu(BTC)
The green fluorescence emission wasofquenched
RGH is in caused by
athe donor–acceptor
rhodamine electronring
spirallactam transfer process.
opening, andThe thegreen fluorescence
RGH-Eu(BTC) emission
color changesof RGH
fromiscolorless
caused
to orange,by awhich
rhodamine
is easyspirallactam
to observeringwithopening,
the naked andeye.
the RGH-Eu(BTC)
The sensor realizes color changes
highly selective
from colorless to orange, which is easy to observe with the naked eye. The sensor realizes
sensing of TNP in acidic analytes (Figure 9).
highly selective sensing of TNP in acidic analytes (Figure 9).

Figure 9.
Figure 9. The
Thesynthetic
syntheticprotocol of RGH–Eu(BTC)
protocol of RGH–Eu(BTC) and its
andprinciple for TNPfor
its principle (orTNP
PA) detection.
(or PA) detection.
Adapted with permission from Ref. [67], 2017, The Royal Society of Chemistry.
Adapted with permission from Ref. [67], 2017, The Royal Society of Chemistry.
Molecules 2023, 28, 4481 12 of 21

Based on the abovementioned contents, fluorescent sensors based on Ln–organic

complexes for nitroaromatics are listed in Table 1.

Table 1. Fluorescent sensors based on Ln–organic complexes for nitroaromatics.

Ln–Organic Complexes Analytes Detection Limit Solvent Mechanism Refs

[EuL(H2 O)3 ]·3H2 O·0.75DMF NB none DMF Static [38]
[Tb(FDA)(DMF)]·DMF NB 0.01666 µg/mL DMF PET + Static [41]
[Eu2 (HPA)6 (phen)2 ]·4H2 O NB - H2 O - [43]
[Eu2 (TFPht)3 (phen)2 (H2 O)2 ]·H2 O NB ppm H2 O PET [51]
[CdCl(L)Eux (H2 O)(DMA)](NO3 )·3DMA NB - H2 O PET [57]
{[Ln(dttpa)1.5 (H2 O)]·xH2 O}n NB 12.5 µM CH3 CN PET + CA [58]
{[Ln2 (NSBPDC)3 (H2 O)4 ]·x(H2 O)}n NB 11.315 µM Ethanol PET + CA [60]
{[Tb(FDA)1.5 (DMF)]·DMF}n NB - DMF PET [61]
[Tb(BTTA)1.5 (H2 O)4.5 ]n NB - Methanol ST [62]
{[Ln2 (L2 )2 (H2 O)5 ]·3H2 O}n NB 1.46 µM Methanol PET [67]
NB 0.489
[Tb2 (TTHA)(H2 O)4 ] PNT 0.609 Ethanol PET [42]
TNP 0.919
[Ln2 (L)2 (H2 O)2 ]·5H2 O 4-NP 7.6 × 10−5 M H2 O CA [40]
[Dy(L)(NO3 )(DMF)3 ] 4-NP 0.0676 µM H2 O CA [52]
[Eu0.5 Tb0.5 (L)(H2 O)3 ]n 4-NP - DMF RET [56]
LZG-Eu/Tb 4-NP 0.0112 µM H2 O CA [63]
4-NP 17 µM
CA + PET +
{Eu2 (TBrTA)3 (H2 O)8 ·2H2 O}n DNP 43.1 µM Ethanol [54]
electrostatic
TNP 74.6 µM
[Nd42 L14 (OH)28 (OAc)84 ] 2-NP 8.22 µM H2 O [46]
[Yb42 L14 (OH)28 (OAc)84 ] 2-NP 27.1 µM CH3 CN PET + other [47]
[Tb4 (2-pyia)6 (HAc)0.5 (2,20 -bipy)
TNP 0.0271 µM H2 O CA + PET + dynamic [39]
(H2 O)4.5 ]·2,20 -bipy·H2 O
[Cd8 Nd4 L8 (OAc)8 ]·4OH TNP 0.55 µM H2 O PET + inner filter effect [44]
[Yb18 (L1 )8 (HL[2])2 (OAc)20 ] TNP 5.1 µM CH3 CN PET + other [45]
[Tb(BDPO)(H2 O)4 ] TNP 0.20 µM H2 O RET [49]
[Eu(BDPO)(H2 O)4 ] TNP 0.21 µM H2 O RET [49]
[Eu(L)6 (DMF)] TNP 3.39 µM CH3 CN PET + CA [50]
[Tb2 (pyia)3 (phen)2 (H2 O)]·H2 O TNP 0.080 µM H2 O CA [55]
[Tb(TCBA)(H2 O)2 ]·DMF TNP 1.64 ppb Ethanol PET [63]
RGH-Eu(BTC) TNP 0.45 µM Ethanol PET + H-bonds [65]
RET + electrostatic
{[Eu2 (HL)2 (H2 O)4 ]·3H2 O}n TNP 2.5 µM H2 O [68]
interaction
4-NTP 21.8 µM
[Eu(TFTA)1.5 (H2 O)2 ]·H2 O 2,4-DNP 31.2 µM Methanol CA + inner filter effect [53]
5-TNP 26.8 µM
La(HTCPE)(H2 O)2 NA 5.68 µM DMF PET + interactions [59]
[Eu2 (dtztp)(OH)2 (DMF)(H2 O)2.5 ]·2H2 O DCN 5.28 ppm H2 O RET + PET [32]
Note: NB: nitrobenzene; 2-NP: 2-nitrophenol; 4-NP: 4-nitrophenol; NA: nitroaniline; DNP: dinitrophenol;
DCN: 2,6-dichloro-4-nitroaniline; TNP: 2,4,6-trinitrophenol; PNT: 4-nitrotoluene.

4. Fluorescence Detection Mechanisms of Ln–Organic Complexes for Nitroaromatics

The fluorescence quenching mechanism of Ln–organic complexes by nitroaromatics
with nitro electron-withdrawing properties may be caused by single or multiple reasons,
which need to be further explored. Due to the presence of electron-withdrawing groups
and the strong oxidant characteristic of nitroaromatics, when these compounds are exposed
to electron-rich complexes, their unoccupied lower π* orbitals are capable of withdrawing
electrons from the excited state of the Ln complex, resulting in fluorescence attenuation.
The mechanism of detection of nitro pollutants by Ln–organic complexes can be divided
into the following types: (1) resonance energy transfer (RET), (2) competition absorption
(CA), (3) photoinduced electron transfer (PET); (4) structural transformation (ST); and
(5) static or dynamic quenching [69].
 Molecules 2023, 28, 4481 13 of 21

4.1. Resonance Energy Transfer (RET)

Resonance energy transfer, as a photoluminescence-sensing mechanism, is a short-
range non-radiative energy transfer process which can significantly improve quenching
efficiency and sensitivity. When the excited donor (fluorophore) induces the acceptor
(analyte) to fluoresce, the fluorescence resonance energy is transferred, while the fluores-
cence intensity of the donor is reduced. Energy transfer is a distance-dependent physical
process, and the efficiency of energy transfer usually hinges on (i) spectral overlap extent,
the emission spectrum and the absorption spectrum of the host and guest; and (ii) dipole–
dipole interaction, and the distance and relative orientation of the host and guest [69]. The
efficiency and rate of energy transfer depends mainly on the degree of spectral overlap
between the donor’s emission spectrum and the acceptor absorption spectrum. If the ener-
gies of the donor and acceptor are close, the energy transfer is significantly likely to occur.
The degree of spectral overlap can be determined by experiment. If the UV-vis absorption
spectrum of the analyte overlaps with the emission spectrum of the complex to a certain
extent, the resonance energy will transfer from the complex to the analyte, resulting in the
fluorescence quenching of the complex. If the overlap between the emission spectrum of
the complex and the absorption spectrum of the analyte is higher, the quenching efficiency
is higher.
Both [Eu(BDPO)(H2 O)4 ] (CUST-623) and [Tb(BDPO)(H2 O)4 ] (CUST-624) based on
N,N0 -bis(3,5-dicarboxyphenyl)-oxalamide (BDPO) could be used as fluorescent sensors
for detecting TNP, and the sensing mechanism could be attributed to RET because their
fluorescence spectra overlap with the ultraviolet visible absorption spectra of TNP [49]. An
Eu/Tb bifunctional metal–organic framework, [Eux Tb1−x (L)(H2 O)3 ]n (H4 LCl = 3-bis(3,5-
dicarboxyphenyl)imidazolium chloride), was synthesized successfully through a solvother-
Molecules 2023, 28, x FOR PEER REVIEW 14 of 22
mal reaction and used as a luminescent sensor to detect 4-NP in DMF and the quenching
efficiency was affected by RET (Figure 10) [66].

Figure 10.10.
Figure Schematic
Schematicrepresentation forthe
representation for thesynthesis
synthesisof of complexes
complexes [Eux[Eu xTb
Tb1-x 1-x(L)(H
(L)(H O)and
2 O)3 2]n 3]n and detec-
detec-
tiontion
of Fe
of Fe cation and 4-NP through fluorescence quenching effect. Adapted with permission from from
3+ cation
3+ and 4-NP through fluorescence quenching effect. Adapted with permission
Ref.Ref.
[56],[56],
2020, The
2020, Royal
The RoyalSociety
Societyof
of Chemistry.
Chemistry.

4.2.4.2. Competition
Competition Absorption(CA)
Absorption (CA)
Competition absorption is the overlap between the excitation spectrum of an Ln–
Competition absorption is the overlap between the excitation spectrum of an Ln–or-
organic complex and the UV-vis absorption spectrum of the analyte. When the excitation
ganic complex
spectrum andcomplex
of the the UV-vis absorption
overlaps spectrum
greatly with of theabsorption
the UV-vis analyte. When the of
spectrum excitation
the
spectrum
analyte,of the
the complex
complex andoverlaps greatly
the analyte with the UV-vis
may competitively absorbabsorption spectrum
the excitation of the an-
light, thereby
alyte, the complex and the analyte may competitively absorb the excitation light, thereby
reducing the total available energy of the complex, resulting in a decrease in the excited
state of the Ln–organic complex. As a result, the fluorescence property of the complex is
quenched. For instance, a Dy organic complex [Dy(L)(NO3)(DMF)3]n (H2L = 2,5-di(1H-
 4.2. Competition Absorption (CA)
Competition absorption is the overlap between the excitation spectrum of an Ln–or-
ganic complex and the UV-vis absorption spectrum of the analyte. When the excitation
Molecules 2023, 28, 4481 spectrum of the complex overlaps greatly with the UV-vis absorption spectrum 14 ofof
21 the an-

alyte, the complex and the analyte may competitively absorb the excitation light, thereby
reducing the total available energy of the complex, resulting in a decrease in the excited
reducing
state of thetheLn–organic
total available energy As
complex. of the complex,
a result, theresulting in a decrease
fluorescence propertyin of
thethe
excited
complex is
state of the Ln–organic complex. As a result, the fluorescence property
quenched. For instance, a Dy organic complex [Dy(L)(NO3)(DMF)3]n (H2L = 2,5-di(1H- of the complex is
quenched. For instance, a Dy organic complex [Dy(L)(NO3 )(DMF)3 ]n (H2 L = 2,5-di(1H-
1,2,4-triazol-1-yl) terephthalic acid) with multi-emission peaks can be used as a lumines-
1,2,4-triazol-1-yl) terephthalic acid) with multi-emission peaks can be used as a luminescent
cent
ratioratio
sensorsensor for and
for 4-NP, 4-NP,
theand the mechanism
sensing sensing mechanism
is attributedistoattributed to aabsorption
a competitive competitive ab-
sorption of excitation
of excitation energies
energies (Figure 11) (Figure
[52]. 11) [52].

Figure
Figure 11.
11. The schematicillustration
The schematic illustration of the
of the mechanism
mechanism of p-NP/ONZ/MNZ/2-MI
of p-NP/ONZ/MNZ/2-MI sensingsensing
by by
[Dy(L)(NO
[Dy(L)(NO33)(DMF)
)(DMF)33]]nn.. Adapted withpermission
Adapted with permission from
from Ref.Ref.
[52],[52],
2021,2021, Elsevier.
Elsevier.

4.3.Photoinduced
4.3. Photoinduced Electron
ElectronTransfer
Transfer(PET)
(PET)
The photoinduced electron transfer (PET) mechanism could be used to explain the
The photoinduced electron transfer (PET) mechanism could be used to explain the
luminescence quenching process of Ln–organic complexes caused by nitroaromatics. The
luminescence
luminescence of quenching process ofcomplex
a lanthanide–organic Ln–organic complexes
is caused causedeffect,
by the antenna by nitroaromatics.
in which the The
luminescence of a lanthanide–organic
energy is transferred complex
from chromogenic organic is caused
ligands bytothe
(sensors) antenna
Ln3+ ions. Foreffect, in which
the PET
mechanism, the conduction band (CB) energy levels of the chemosensors are higher than
the LUMO levels of the explosives. Thus, the excitation energy of the chemosensors may
be consumed by their electron transfer to the electron-deficient nitro explosives, resulting
in the luminescence quenching of the lanthanide–organic complexes at the lowest LUMO
energy value.
Various interactions in the metal coordination polymer (such as hydrogen bonding or
π-π packing) with the host and guest of the analyte may facilitate the photoelectron transfer
process during photoexcitation. PET is a redox process in which excited photoelectrons are
transferred from the donor to the electron-deficient ground-state receptor. When the lowest
unoccupied molecular orbital (LUMO) energy of the donor (fluorophores) is higher than the
LUMO energy of the acceptor (analytical compound), photoelectrons may be transferred
from the excited donor to the ground-state receptor, resulting in the fluorescence quenching
of the donor. Correspondingly, when the LUMO orbital energy of the donor is lower
than the LUMO orbital energy of the recipient, photoelectrons may be transferred from
the recipient to the donor, resulting in the enhanced fluorescence of the donor. Then,
a recombination of charges in the ground state of the donor or acceptor occurs. Therefore,
the complexation between the analyte and the sensor probe material will cause changes
in the highest occupied molecular orbital (HOMO) and LUMO of the probe, which will
greatly affect the efficiency of the sensor probe.
Generally, the energy of the conduction band (CB) of an electron-rich MOF is higher
than the lowest unoccupied orbital energy of a nitro compound. When the excited electrons
of the CB of MOFs are transferred to the LUMO, the nitro compound will cause fluores-
cence quenching, and the fluorescence-quenching performance will be improved with the
Molecules 2023, 28, 4481 15 of 21

decrease in LUMO orbital energy. That is to say, the PET leads to fluorescence quench-
ing. A lot of fluorescence-quenching examples of Ln–organic sensors for nitroaromatics
are ascribed to the PET mechanism. For instance, {[Eu2 (L2)2 (H2 O)5 ]·3H2 O}n constructed
from 5-(30 ,50 -dicarboxylphenyl) picolinic acid (L2) by an in-situ decarboxylation reaction
under hydrothermal conditions was used as a multifunctional sensor to detect Cu2+ ion,
MnO4 − anion, and NB. The results showed a high sensitivity and selectivity through the
fluorescence-quenching effect (Figure 12). For the sensing of NB, a possible mechanism
Molecules 2023, 28, x FOR PEER REVIEW 16 [68]
may be allied to the PET from an electron-rich excited MOF to the electron-deficient NB of 22
(Table 1).

Figure 12.(a)
Figure12. (a)Emission
Emissionspectra
spectraofof{[Eu
{[Eu 2 (L2) 2 (H
2(L2) 2 O)
2(H 2O) ·3H22O}nn (Eu-MOF) in
55]]·3H in various
various concentrations
concentrationsofof
NB, (b) the Stern–Volmer plot of I /I versus the concentration of nitrobenzene for
NB, (b) the Stern–Volmer plot of I0 /I versus the concentration of nitrobenzene for Eu-MOF, (c) the S–V
0 Eu-MOF, (c) the
S–V curve
curve of I0 /Iofversus
I0/I versus the concentration
the concentration of NBoffor NBEu-MOF
for Eu-MOF
at lowatconcentration,
low concentration, (d)
(d) the the lumines-
luminescence
cence intensity ( 5D0 → 7F2) of five recyclable experiments of sensing for nitrobenzene in MeOH so-
5 7
intensity ( D0 → F2 ) of five recyclable experiments of sensing for nitrobenzene in MeOH solution.
lution. Adapted with permission from Ref. [68], 2020, American Chemical Society.
Adapted with permission from Ref. [68], 2020, American Chemical Society.

4.4.Structural
4.4. StructuralTransformation
TransformationMechanism
Mechanism(ST)
(ST)
Thestructural
The structuraltransformation
transformation mechanism
mechanism is when
is when guestguest molecules
molecules enter enter
the poretheskele-
pore
skeleton
ton of a metal–organic
of a metal–organic complex complex
(host) to(host) to generate
generate guest–host
guest–host interactions,
interactions, thereby
thereby leading
to the alteration
leading in the coordination
to the alteration environment
in the coordination of metalofions
environment andions
metal even
andstructural defor-
even structural
mation, resulting
deformation, in significant
resulting changeschanges
in significant in the luminescence of the metal–organic
in the luminescence complex.
of the metal–organic
This case can
complex. Thisbecase
applied
can beto the selective
applied to thedetection
selective ofdetection
analytes. of
The host–guest
analytes. Theinteraction
host–guest
promotes or interrupts
interaction promotes or theinterrupts
sensitization
thepathways of the
sensitization lanthanide
pathways of ion
theand, therefore,
lanthanide ionleads
and,
to the enhancement
therefore, or quenching
leads to the enhancement of the
or luminescence,
quenching of the respectively [70]. An
luminescence, investigation
respectively [70].
elucidated the detection
An investigation principle
elucidated theofdetection
luminescence quenching
principle in a [Tb(BTTA)
of luminescence quenching
1.5 (H2 O) in]na
4.5
sensor based on 2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acid (BTTA)
[Tb(BTTA)1.5(H2O)4.5]n sensor based on 2,5-bis(1H-1,2,4-triazol-1-yl) terephthalic acidfor NB. Through
multireference
(BTTA) for NB.CASSCF/NEVPT2
Through multireference calculations, it demonstrated
CASSCF/NEVPT2 the valueitof
calculations, host–guest-
demonstrated
interaction simulations and the rate constants of the radiative and nonradiative
the value of host–guest-interaction simulations and the rate constants of the radiative and processes in
understanding and elucidating
nonradiative processes the sensing mechanism
in understanding and elucidatingin Ln-MOF sensors
the sensing (Figure 13)in[62].
mechanism Ln-
MOF sensors (Figure 13) [62].
Molecules 2023, 28, x FOR PEER REVIEW
Molecules 2023, 28, 4481 16 of 21

Figure13.
Figure 13.Energy
Energy level
level diagram
diagram depicting
depicting thelikely
the most mostsensitization
likely sensitization
and emissionand emission proc
processes
for [Tb(BTTA)
[Tb(BTTA)1.51.5 (H
(H2O) O)
2 4.5 ]
]n/NB.
4.5 n /NB. Intersystem crossing, phosphorescence, and fluorescence
Intersystem crossing, phosphorescence, and fluorescence rates are rates a
represented
sented by by theletters
the letters kkISC , kP ,Pand
ISC, k
kF , k
, and respectively, while ET stands for energy transfer and BET is
F, respectively, while ET stands for energy transfer an
back energy transfer (BET). Adapted with
back energy transfer (BET). Adapted with permissionpermission from Ref. [62],from
2022, American
Ref. [62],Chemical Society.
2022, American Chem
ciety.
4.5. Static or Dynamic Quenching Mechanism (SY)
Static quenching is the formation of a non-fluorescent ground-state complex between
4.5.complex
the Static orandDynamic Quenching
the analyte, Mechanism
which absorbs light (SY)
but does not emit photons and im-
mediately returns to the ground state. Dynamic quenching is the transfer of electrons
Static quenching is the formation of a non-fluorescent ground-state complex b
between the quencher and the sensor through excited-state collisions. Both are generally
the complex by
distinguished and the analyte,
changes which decay
in fluorescence absorbs lightand
lifetime buttwodoes not emitprocesses.
quenching photons and i
ately returns
Fluorescence to thespectroscopy
lifetime ground state. Dynamic
is a potential quenching
technique is the transfer
to distinguish betweenofstatic
electrons b
the quencher
quenching and thequenching.
and dynamic sensor through excited-state
The fluorescence lifetimecollisions. Bothquench-
spectra of static are generally
ing before and after the introduction of an analyte are similar, and
guished by changes in fluorescence decay lifetime and two quenching processes. dynamic quenching
decreases before and after the introduction of the analyte and, thereby, results in the
cence lifetime spectroscopy is a potential technique to distinguish between static qu
fluorescence-quenching phenomenon of the complexes. Under the static mechanism,
aand dynamic quenching.
non-fluorescent The fluorescence
complex is formed lifetimeand
between the complex spectra of static
the analyte, andquenching
fluores- bef
after derived
cence the introduction
from the same of an analyte
complex. are similar,
However, and dynamic
the fluorescence lifetimequenching
was found todecrease
decrease
and afterin the
dynamic quenching,of
introduction because the collisions
the analyte between the
and, thereby, complex
results in and
thethe analyte
fluorescence-qu
reduced the excited states. As shown in Figure 14, after adding TNP into a 2D Tb–organic
phenomenon of the complexes. Under the static mechanism, a non-fluorescent com
network [Tb2 (pyia)3 (phen)2 (H2 O)]·H2 O (H2 pyia = 5-(pyridine-2-ylmethoxy) isophthalic
formed
acid, phenbetween the complex and
= 1,10-phenanthroline) the analyte,
solution, and fluorescence
its fluorescence decay lifetime derived from
was 1.941 ns, the sam
plex. However,
reflecting the fluorescence
a dynamic-quenching lifetime
process compared was found
with to decrease
the average in dynamic
fluorescence lifetime quench
value (1.402 ns) [55].
cause the collisions between the complex and the analyte reduced the excited st
shown in Figure 14, after adding TNP into a 2D Tb–organic n
[Tb2(pyia)3(phen)2(H2O)]⋅H2O (H2pyia = 5-(pyridine-2-ylmethoxy) isophthalic acid,
1,10-phenanthroline) solution, its fluorescence decay lifetime was 1.941 ns, reflectin
namic-quenching process compared with the average fluorescence lifetime value (1
[55].
Molecules 2023, 28, 4481
x FOR PEER REVIEW 1817of
of 22
21

Figure 14.
Figure 14. (a)
(a) Fluorescence
Fluorescence intensity
intensity of
of Tb
Tb complex
complex dispersed
dispersed in
in aqueous
aqueous solutions
solutions of
of different
different nitro
nitro
explosives at 550 nm (λex = 310 nm). (b) Tb complex dispersed in aqueous solutions of different
explosives at 550 nm (λex = 310 nm). (b) Tb complex dispersed in aqueous solutions of different
concentrations of TNP at 550 nm; changes in fluorescence intensity. (c) S–V plot of TNP concentra-
concentrations of TNP at 550 nm; changes in fluorescence intensity. (c) S–V plot of TNP concentration
tion and fluorescence intensity at low concentrations. (d) Interference of inorganic anions on Tb
and fluorescence intensity at low concentrations. (d) Interference of inorganic anions on Tb complex
complex fluorescence sensing TNP. Adapted with permission from Ref. [55], 2022, Elsevier.
fluorescence sensing TNP. Adapted with permission from Ref. [55], 2022, Elsevier.
For many nitroaromatics, the fluorescence quenching of lanthanide compounds is
For many nitroaromatics, the fluorescence quenching of lanthanide compounds is
mostly caused by a combination of various mechanisms. For example, the Nd42 cluster
mostly caused by a combination of various mechanisms. For example, the Nd42 clus-
[Nd42L14(OH)28(OAc)84] (HL = 3-methoxysalicylaldehyde) exhibits interesting NIR lumi-
ter [Nd42 L14 (OH)28 (OAc)84 ] (HL = 3-methoxysalicylaldehyde) exhibits interesting NIR
nescence-sensing behavior to nitro explosives, which may be explained by PET and RET
luminescence-sensing behavior to nitro explosives, which may be explained by PET and
mechanisms [46].[46].
TheTheEu–organic
Eu–organiccomplex
complex {[Eu
{[Eu22(HL)
(HL)22(H
(H2O) 4]·3H2O}n (H4L = 3,3′,5,5′-
0 0
RET mechanisms 2 O)4 ]·3H2 O}n (H4 L = 3,3 ,5,5 -
azoxybenzenetetracarboxylic acid) can detect TNP with the high selectivity,
azoxybenzenetetracarboxylic acid) can detect TNP with the high selectivity, which can be which can be
assigned to
assigned tothe
thecombined
combinedeffects
effectsofof electron
electron andand energy
energy transfer
transfer mechanisms
mechanisms as well
as well as
as elec-
electrostatic interactions [71]. The emission of another Eu-MOF
trostatic interactions [71]. The emission of another Eu-MOF {Eu2 (TBrTA)3 (H2 O)8 ·2H2 O}n {Eu 2(TBrTA)3

(Hmore
is 2O)8·2H2O}n is more than 85% quenched by nitroaromatic compounds (NACs) such as
than 85% quenched by nitroaromatic compounds (NACs) such as 4-nitrophenol,
4-nitrophenol, and
dinitrophenol, dinitrophenol, and(picric
trinitrophenol trinitrophenol
acid) with(picric acid) with
competitive competitive
absorption, absorp-
photoinduced
electron transfer, and electrostatic processes the main mechanisms of quenching [54]. of
tion, photoinduced electron transfer, and electrostatic processes the main mechanisms
quenching [54].
5. Conclusions and Outlook
5. Conclusions
In summary, and Outlook Ln–organic complex-based luminescent materials are eluci-
crystalline
datedInand
summary,
analyzed crystalline Ln–organic
in this review. complex-based
According luminescent
to the different materials
dimensions, are eluci-
lanthanide–
dated and
organic analyzed
complexes inbe
can this review.into
classified According to the
0D (discrete different 1D,
molecule), dimensions,
2D and 3D lanthanide–
structures.
Correspondingly,
organic complexesonly canabefew 0D, 1D into
classified and 0D
2D (discrete
Ln complexes with luminescent
molecule), 1D, 2D and 3D properties are
structures.
found, and most luminescent
Correspondingly, only a few Ln–organic
0D, 1D andcomplexes have the with
2D Ln complexes 3D structure. Due properties
luminescent to their lu-
minescent
are found,property,
and most Ln-organic
luminescentcomplex-based
Ln–organicsensors can be
complexes used
have to 3D
the detect nitroaromatics,
structure. Due to
including nitrobenzene
their luminescent (NB),Ln-organic
property, nitrophenolcomplex-based
(4-NP or 2-NP),sensors
and trinitrophenol
can be used(TNP) at very
to detect ni-
low concentrations.
troaromatics, Moreover,
including six main(NB),
nitrobenzene fluorescence-detection
nitrophenol (4-NPmechanisms
or 2-NP), and(RET, CA, PET,
trinitrophe-
ST,
nol SY)
(TNP)of Ln–organic
at very low complexes for nitroaromatics
concentrations. Moreover, sixaremainaddressed. This review will
fluorescence-detection help
mecha-
readers to better understand the fluorescence sensing of lanthanide–organic
nisms (RET, CA, PET, ST, SY) of Ln–organic complexes for nitroaromatics are addressed.complexes and
their quenching mechanisms with nitroarenes.
This review will help readers to better understand the fluorescence sensing of lanthanide–
organic complexes and their quenching mechanisms with nitroarenes.
Molecules 2023, 28, 4481 18 of 21

In term of structural characteristics, lanthanide–organic-complex sensors possess,

mainly, three-dimensional stable frameworks and large porosity. Investigations showed
that low-dimensional lanthanide coordination polymers also exhibit good sensing per-
formance due to their large specific surface area and the presence of large numbers of
weak interactions. Therefore, it is necessary to explore more low-dimensional lanthanide
coordination polymers as the sensing materials for the detection of nitroarenes with very
low concentration. Due to the elusive synthetic conditions, lanthanide coordination poly-
mer sensors with mixed ligands or heterometals are less reported. The rich structural
features and better sensing properties of heterometallic Ln–organic complexes with mixed
ligands motivate us to rationally design and prepare more such substances in the future
for application in luminescence sensing. On the other hand, we hope that more and more
nitroaromatics can be easily detected by Ln–organic complexes to increase the detection
range and capability of nitro pollutants.

Funding: This research was funded by the National Natural Science Foundation of China [No.
22063010] and the Youth Innovation Team of Shaanxi Universities.
Data Availability Statement: No further data are available.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Fan, M.; Sun, B.; Li, X.; Pan, Q.; Sun, J.; Ma, P.; Su, Z. Highly Fluorescent Cadmium Based Metal–Organic Frameworks for Rapid
Detection of Antibiotic Residues, Fe3+ and Cr2 O7 2− Ions. Inorg. Chem. 2021, 60, 9148–9156. [CrossRef]
2. Liu, W.; Li, N.N.; Zhang, X.; Zhao, Y.; Zong, Z.; Wu, R.; Tong, J.; Bi, C.; Shao, F.; Fan, Y. Four Zn(II)-MOFs as Highly Sensitive
Chemical Sensor for the Rapid Detection of Tetracycline, o-Nitro Phenol, Cr2 O7 2− /PO4 3− , Fe3+ /Al3+ in Water Environment.
Cryst. Growth Des. 2021, 21, 5558–5572. [CrossRef]
3. Li, J.; Tian, J.; Yu, H.; Fan, M.; Li, X.; Liu, F.; Sun, J.; Su, Z. Controllable Synthesis of Metal–Organic Frameworks Based on
Anthracene Ligands for High-Sensitivity Fluorescence Sensing of Fe3+ , Cr2 O7 2− , and TNP. Cryst. Growth Des. 2022, 22, 2954–2963.
[CrossRef]
4. Ramu, A.G.; Salla, S.; Chandrasekaran, S.; Silambarasan, P.; Gopi, S.; Seo, S.-Y.; Yun, K.; Choi, D. A facile synthesis of metal
ferrites and their catalytic removal of toxic nitro-organic pollutants. Environ. Pollut. 2021, 270, 116063. [CrossRef] [PubMed]
5. Toxicological Profile for Nitrobenzene, Agency for Toxic Substances and Disease Registry U.S. Public Health Service. 1990.
Available online: https://www.atsdr.cdc.gov/ToxProfiles/tp140.pdf (accessed on 28 April 2023).
6. Guria, M.K.; Majumdar, M.; Bhattacharyya, M. Green synthesis of protein capped nano-gold particle: An excellent recyclable
nano-catalyst for the reduction of nitro-aromatic pollutants at higher concentration. J. Mol. Liq. 2016, 222, 549–557. [CrossRef]
7. Luo, J.; Cong, J.; Liu, J.; Gao, Y.; Liu, X. A facile approach for synthesizing molecularly imprinted graphene for ultrasensitive and
selective electrochemical detecting 4-nitrophenol. Anal. Chim. Acta 2015, 864, 74–84. [CrossRef] [PubMed]
8. Dang, D.K.; Sundaram, C.; Ngo, Y.L.T.; Choi, W.M.; Chung, J.S.; Kim, E.J.; Hur, S.H. Pyromellitic acid-derived highly fluorescent
N-doped carbon dots for the sensitive and selective determination of 4-nitrophenol. Dyes Pigm. 2019, 165, 327–334. [CrossRef]
9. Rajak, R.; Saraf, M.; Verma, S.K.; Kumar, R.; Mobin, S.M. Dy(III)-Based Metal–Organic Framework as a Fluorescent Probe for
Highly Selective Detection of Picric Acid in Aqueous Medium. Inorg. Chem. 2019, 58, 16065–16074. [CrossRef] [PubMed]
10. Fan, M.Y.; Yu, H.H.; Fu, P.; Su, Z.M.; Li, X.; Hu, X.L.; Gao, F.W.; Pan, Q.Q. Luminescent Cd(II) metal-organic frameworks with
anthracene nitrogen-containing organic ligands as novel multifunctional chemosensors for the detection of picric acid, pesticides,
and ferric ions. Dyes Pigm. 2021, 185, 108834. [CrossRef]
11. Zheng, Y.; Li, Q.; Wang, C.; Su, M. Enhanced Turn-On Fluorescence Detection of Aqueous Lead Ions with Size-Shrinkable
Hydrogels. ACS Omega. 2021, 6, 11897–11901. [CrossRef]
12. Wang, J.-X.; Yin, J.; Shekhah, O.; Bakr, O.M.; Eddaoudi, M.; Mohammed, O.F. Energy Transfer in Metal–Organic Frameworks for
Fluorescence Sensing. ACS Appl. Mater. Interfaces. 2022, 14, 9970–9986. [CrossRef] [PubMed]
13. Dutta, A.; Singh, A.; Wang, X.; Kumar, A.; Liu, J. Luminescent sensing of nitroaromatics by crystalline porous materials.
CrystEngComm 2020, 22, 7736–7781. [CrossRef]
14. Yang, S.X.; Hu, J.S.; Zhang, J.; He, T.C.; Zhang, L.Y.; Chen, H. A high selectively and sensitively fluorescent Eu metal-organic
framework for sensing nitro aromatic compounds in aqueous media. Inorg. Chim. Acta 2022, 536, 120914. [CrossRef]
15. Zhang, J.; Hu, J.; Sun, C.; Li, X. A thermal and pH stable fluorescent metal-organic framework sensor for high selectively and
sensitively sensing nitro aromatic compounds in aqueous media. J. Mol. Struct. 2021, 1245, 131059. [CrossRef]
16. Silver, B. Atomic Absorption Spectroscopy Reveals Anomalous Transfer of Heavy Metal across a Water/1,2-DCE Interface. Port.
Electrochim. Acta 2021, 39, 415–420. [CrossRef]
Molecules 2023, 28, 4481 19 of 21

17. Ruella Oliveira, S.; Tuttis, K.; Rita Thomazela Machado, A.; Cristina de Souza Rocha, C.; Maria Greggi Antunes, L.; Barbosa, F.
Cell-to-cell heterogeneous association of prostate cancer with gold nanoparticles elucidated by single-cell inductively coupled
plasma mass spectrometry. Microchem. J. 2022, 177, 107275. [CrossRef]
18. Lamei, N.; Ezoddin, M.; Kakavandi, N.R.; Abdi, K.; Ghazi-khansari, M. Ultrasound-Assisted Switchable Solvent in Determination
of Quaternary Ammonium Herbicide Paraquat in Biological, Environmental Water, and Apple Juice Samples Using Chemical
Reduction Process Coupled to GC–MS Detection. Chromatographia 2018, 81, 923–930. [CrossRef]
19. Gruznov, V.M.; Baldin, M.N.; Makas, A.L.; Titov, B.G. Progress in methods for the identification of explosives in Russia. J. Anal.
Chem. 2011, 66, 1236–1246. [CrossRef]
20. Brown, K.E.; Greenfield, M.T.; McGrane, S.D.; Moore, D.S. Advances in explosives analysis–part I: Animal, chemical, ion, and
mechanical methods. Anal. Bioanal. Chem. 2016, 408, 35–47. [CrossRef]
21. Brown, K.E.; Greenfield, M.T.; McGrane, S.D.; Moore, D.S. Advances in explosives analysis–part II: Photon and neutron methods.
Anal. Bioanal. Chem. 2016, 408, 49–65. [CrossRef]
22. Liu, Y.-Y.; Xu, X.; Xin, J.-W.; Ghulamb, M.; Fan, J.; Dong, X.; Qiu, L.-L.; Xue, M.; Meng, Z.-H. Molecularly imprinted colloidal
array for the high-throughput screening of explosives. Chin. J. Anal. Chem. 2023, 51, 100215. [CrossRef]
23. Bairy, G.; Dey, A.; Dutta, B.; Ray, P.P.; Sinha, C. 2D Cd(II)-MOF of Pyridyl-Imidazoquinazoline: Structure, Luminescence, and
Selective Detection of TNP and Fabrication of Semiconducting Devices. Cryst. Growth Des. 2022, 22, 3138–3147. [CrossRef]
24. Razavi, S.A.A.; Morsali, A.; Piroozzadeh, M. A Dihydrotetrazine-Functionalized Metal–Organic Framework as a Highly Selective
Luminescent Host–Guest Sensor for Detection of 2,4,6-Trinitrophenol. Inorg. Chem. 2022, 61, 7820–7834. [CrossRef] [PubMed]
25. Goswami, R.; Mandal, S.C.; Pathak, B.; Neogi, S. Guest-Induced Ultrasensitive Detection of Multiple Toxic Organics and Fe3+
Ions in a Strategically Designed and Regenerative Smart Fluorescent Metal–Organic Framework. ACS Appl. Mater. Interfaces 2019,
11, 9042–9053. [CrossRef]
26. Li, H.-Y.; Zhao, S.-N.; Zang, S.-Q.; Li, J. Functional metal–organic frameworks as effective sensors of gases and volatile compounds.
Chem. Soc. Rev. 2020, 49, 6364–6401. [CrossRef] [PubMed]
27. Verbitskiy, E.V.; Rusinov, G.L.; Chupakhin, O.N.; Charushin, V.N. Design of fluorescent sensors based on azaheterocyclic push-pull
systems towards nitroaromatic explosives and related compounds: A review. Dye. Pigment. 2020, 180, 108414. [CrossRef]
28. Ahmed, R. Review: Fluorophores for detecting Nitroaromatic Compounds, Picric Acid. Int. J. Multidiscip. Res. Anal. 2023, 6,
1119–1131. [CrossRef]
29. Svalova, T.S.; Saigushkina, A.A.; Verbitskiy, E.V.; Chistyakov, K.A.; Varaksin, M.V.; Rusinov, G.L.; Charushin, V.N.; Kozitsina, A.N.
Rapid and sensitive determination of nitrobenzene in solutions and commercial honey samples using a screen-printed electrode
modified by 1,3-/1,4-diazines. Food Chem. 2022, 372, 131279. [CrossRef]
30. Zhao, P.; Liu, Y.; He, C.; Duan, C. Synthesis of a Lanthanide Metal–Organic Framework and Its Fluorescent Detection for
Phosphate Group-Based Molecules Such as Adenosine Triphosphate. Inorg. Chem. 2022, 61, 3132–3140. [CrossRef]
31. Sun, Y.-Q.; Cheng, Y.; Yin, X.-B. Dual-Ligand Lanthanide Metal–Organic Framework for Sensitive Ratiometric Fluorescence
Detection of Hypochlorous Acid. Anal. Chem. 2021, 93, 3559–3566. [CrossRef]
32. Wang, G.-D.; Li, Y.-Z.; Shi, W.-J.; Zhang, B.; Hou, L.; Wang, Y.-Y. A robust cluster-based Eu-MOF as multi-functional fluorescence
sensor for detection of antibiotics and pesticides in water. Sens. Actuators B Chem. 2021, 331, 129377. [CrossRef]
33. Xu, M.-Y.; Liang, G.-Y.; Feng, J.-S.; Liang, G.-M.; Wang, X.-J. Temperature-Induced Structural Transformations of Lanthanide
Coordination Polymers Based on a Semirigid Tricarboxylic Acid Ligand: Crystal Structures and Luminescence Properties. Cryst.
Growth Des. 2022, 22, 1583–1593. [CrossRef]
34. Xiao, J.; Liu, M.; Tian, F.; Liu, Z. Stable Europium-based Metal–Organic Frameworks for Naked-eye Ultrasensitive Detecting
Fluoroquinolones Antibiotics. Inorg. Chem. 2021, 60, 5282–5289. [CrossRef]
35. Bodman, S.E.; Butler, S.J. Advances in anion binding and sensing using luminescent lanthanide complexes. Chem. Sci. 2021, 12,
2716–2734. [CrossRef]
36. Sahoo, S.; Mondal, S.; Sarma, D. Luminescent Lanthanide Metal-Organic Frameworks (Ln MOFs): A Versatile Platform towards
Organomolecule Sensing. Coord. Chem. Rev. 2022, 470, 214707. [CrossRef]
37. Chai, H.M.; Yan, J.L.; Zhang, G.Q.; Wang, J.X.; Ren, Y.X.; Gao, L.J. Five Mesoporous Lanthanide Metal-Organic Frameworks:
Syntheses, Structures, and Fluorescence Sensing of Fe3+ , Cr2 O7 2− , and H2 O2 and Electrochemical Sensing of Trinitrophenol.
Inorg. Chem. 2022, 61, 7286–7295. [CrossRef] [PubMed]
38. Gao, R.C.; Guo, F.S.; Bai, N.N.; Wu, Y.L.; Yang, F.; Liang, J.Y.; Li, Z.J.; Wang, Y.Y. Two 3D Isostructural Ln(III)-MOFs: Displaying
the Slow Magnetic Relaxation and Luminescence Properties in Detection of Nitrobenzene and Cr2 O7 2− . Inorg. Chem. 2016, 55,
11323–11330. [CrossRef]
39. Gao, T.; Ma, Z.; Ren, Y.; Wang, Z.; Zhang, M.; Chen, X.; Wang, J. High sensitive fluorescent sensing and photocatalytic degradation
performance of two-dimensional Tb-organic network. J. Rare Earths 2023, in press. [CrossRef]
40. Ma, J.J.; Liu, W.S. Effective luminescence sensing of Fe3+ , Cr2 O7 2− , MnO4 − and 4-nitrophenol by lanthanide metal–organic
frameworks with a new topology type. Dalton Trans. 2019, 48, 12287–12295. [CrossRef]
41. Yue, D.; Zhao, D.; Zhang, J.; Zhang, L.; Jiang, K.; Zhang, X.; Cui, Y.; Yang, Y.; Chen, B.; Qian, G. A luminescent cerium
metal–organic framework for the turn-on sensing of ascorbic acid. Chem. Commun. 2017, 53, 11221–11224. [CrossRef]
42. Zhang, N.; Li, B.; Wang, X.; Liu, D.; Han, X.; Bai, F.; Xing, Y. High-efficiency fluorescent probe constructed by triazine polycar-
boxylic acid for detecting nitro compounds. Inorg. Chim. Acta 2020, 507, 119591. [CrossRef]
Molecules 2023, 28, 4481 20 of 21

43. Chen, F.; Wang, J.; Dong, M.W.; Zhang, S.L.; Wu, C.P.; Liu, J.Q. Five lanthanide supramolecular frameworks based on mixed
3-(4-hydroxyphenyl)propanoic acid and 1,10-phenanthroline tectons: Crystal structures and luminescent properties. J. Mol. Struct.
2019, 1177, 117–123. [CrossRef]
44. Ma, Y.; Yang, X.; Niu, M.; Hao, W.; Shi, D.; Schipper, D. High-Nuclearity Cd(II)–Nd(III) Nanowheel with NIR Emission Sensing of
Metal Cations and Nitro-Based Explosives. Cryst. Growth Des. 2021, 21, 2821–2827. [CrossRef]
45. Ma, Y.; Yang, X.; Niu, M.; Shi, D.; Schipper, D. One high-nuclearity Yb(III) nanoring with NIR luminescent sensing towards
antibiotics and explosives. J. Lumin. 2022, 241, 118494. [CrossRef]
46. Shi, D.; Yang, X.; Chen, H.; Jiang, D.; Liu, J.; Ma, Y.; Schipper, D.; Jones, R.A. Large Ln42 coordination nanorings: NIR luminescence
sensing of metal ions and nitro explosives. Chem. Comm. 2019, 55, 13116–13119. [CrossRef] [PubMed]
47. Shi, D.; Yang, X.; Chen, H.; Ma, Y.; Schipper, D.; Jones, R.A. Self-assembly of luminescent 42-metal lanthanide nanowheels with
sensing properties towards metal ions and nitro explosives. J. Mater. Chem. C 2019, 7, 13425–13431. [CrossRef]
48. Jiang, D.; Yang, X.; Zheng, X.; Bo, L.; Zhu, T.; Chen, H.; Zhang, L.; Huang, S. Self-assembly of luminescent 12-metal Zn–Ln planar
nanoclusters with sensing properties towards nitro explosives. J. Mater. Chem. C 2018, 6, 8513–8521. [CrossRef]
49. Wang, S.; Sun, B.; Su, Z.; Hong, G.; Li, X.; Liu, Y.; Pan, Q.; Sun, J. Lanthanide-MOFs as multifunctional luminescent sensors. Inorg.
Chem. Front. 2022, 9, 3259–3266. [CrossRef]
50. Liu, Y.; Sun, Q.; Zhou, H.; Gao, H.; Li, D.; Li, Y. One-dimensional Europium-coordination polymer as luminescent sensor for
highly selective and sensitive detection of 2,4,6-trinitrophenol. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2022, 264, 120303.
[CrossRef]
51. Li, J.J.; Fan, T.T.; Qu, X.L.; Han, H.L.; Li, X. Temperature-induced 1D lanthanide polymeric frameworks based on Lnn (n = 2, 2, 4,
6) cores: Synthesis, crystal structures and luminescence properties. Dalton Trans. 2016, 45, 2924–2935. [CrossRef]
52. Liu, W.; Liu, G.; Gao, G.; Gao, Z.; Zhang, Y.; Wu, S.; Gao, E.; Zhu, M. A new dysprosium (III)-Organic framework as a ratiometric
luminescent sensor for Nitro-compounds and antibiotics in aqueous solutions. Inorg. Chem. Commun. 2021, 133, 108952.
[CrossRef]
53. Smith, J.A.; Singh-Wilmot, M.A.; Carter, K.P.; Cahill, C.L.; Ridenour, J.A. Supramolecular assembly of lanthanide-2,3,5,6-
tetrafluoroterephthalic acid coordination polymers via fluorine· · · fluorine interactions: A platform for luminescent detection of
Fe3+ and nitroaromatic compounds. New J. Chem. 2020, 44, 12317–12330. [CrossRef]
54. Smith, J.A.; Singh-Wilmot, M.A.; Carter, K.P.; Cahill, C.L.; Ridenour, J.A. Lanthanide-2,3,5,6-Tetrabromoterephthalic Acid Metal–
Organic Frameworks: Evolution of Halogen···Halogen Interactions across the Lanthanide Series and Their Potential as Selective
Bifunctional Sensors for the Detection of Fe3+ , Cu2+ , and Cryst. Growth Des. 2019, 19, 305–319. [CrossRef]
55. Gao, T.; Ren, Y.; Wang, Z.; Zhang, M.; Cao, J.; Wang, J. A multi-functional Tb-organic network featuring high selectivity
fluorescent sensing for Fe3+ , Cr2 O7 2− , tetracycline and 2,4,6-trinitrophenol in aqueous solution. J. Solid State Chem. 2022,
309, 123002. [CrossRef]
56. Cheng, X.; Hu, J.; Li, J.; Zhang, M. Tunable emission and selective luminescence sensing for nitro- pollutants and metal ions based
on bifunctional lanthanide metal-organic frameworks. J. Lumin. 2020, 221, 117100. [CrossRef]
57. Zhang, S.-R.; Du, D.-Y.; Qin, J.-S.; Li, S.-L.; He, W.-W.; Lan, Y.-Q.; Su, Z.-M. 2D Cd(II)–Lanthanide(III) Heterometallic–Organic
Frameworks Based on Metalloligands for Tunable Luminescence and Highly Selective, Sensitive, and Recyclable Detection of
Nitrobenzene. Inorg. Chem. 2014, 53, 8105–8113. [CrossRef] [PubMed]
58. Wang, A.; Zhang, Y.; Lu, L.; Zhu, M.; Yuan, C.; Feng, S. Seven Ln(III) coordination polymers with two kinds of geometric
coordination but the same 3D topological property: Luminescence sensing and magnetic property. Dalton Trans. 2022, 51,
12324–12333. [CrossRef]
59. Song, N.; Li, W.; Luo, W.; Zhai, Z.; Wang, S.; Huai, R.; Zhang, D.; Zhou, Z.; Yang, L. Efficient and selective fluorescence sensing
of nitro-containing aromatic compounds by a binuclear lanthanide-based metal-organic framework. J. Solid State Chem. 2022,
316, 123568. [CrossRef]
60. Ren, L.L.; Cui, Y.Y.; Cheng, A.L.; Gao, E.Q. Water-stable lanthanide-based metal-organic frameworks for rapid and sensitive
detection of nitrobenzene derivatives. J. Solid State Chem. 2019, 270, 463–469. [CrossRef]
61. Liu, W.; Li, D.; Wang, F.; Chen, X.; Wang, X.; Tian, Y. A luminescent lanthanide MOF as highly selective and sensitive fluorescent
probe for nitrobenzene and Fe3+ . Opt. Mater. 2022, 123, 111895. [CrossRef]
62. Hidalgo-Rosa, Y.; Mena-Ulecia, K.; Treto-Suárez, M.A.; Schott, E.; Páez-Hernández, D.; Zarate, X. Expanding the Knowl-
edge of the Selective-Sensing Mechanism of Nitro Compounds by Luminescent Terbium Metal–Organic Frameworks through
Multiconfigurational ab Initio Calculations. J. Phys. Chem. C 2022, 126, 7040–7050. [CrossRef] [PubMed]
63. Lin, Z.G.; Song, F.Q.; Wang, H.; Song, X.Q.; Yu, X.X.; Liu, W.S. The construction of a novel luminescent lanthanide framework for
the selective sensing of Cu2+ and 4-nitrophenol in water. Dalton Trans. 2021, 50, 1874–1886. [CrossRef] [PubMed]
64. Kim, D.; Lynch, V.; Nielsen, K.; Johnsen, C.; Jeppesen, J.; Sessler, J. A chloride-anion insensitive colorimetric chemosensor for
trinitrobenzene and picric acid. Anal. Bioanal. Chem. 2009, 395, 393–400. [CrossRef]
65. Herrera-Chacon, A.; Gonzalez-Calabuig, A.; del Valle, M. Dummy Molecularly Imprinted Polymers Using DNP as a Template
Molecule for Explosive Sensing and Nitroaromatic Compound Discrimination. Chemosensors 2021, 9, 255. [CrossRef]
66. Xu, W.; Chen, H.; Xia, Z.; Ren, C.; Han, J.; Sun, W.; Wei, Q.; Xie, G.; Chen, S. A Robust TbIII-MOF for Ultrasensitive Detection of
Trinitrophenol: Matched Channel Dimensions and Strong Host–Guest Interactions. Inorg. Chem. 2019, 58, 8198–8207. [CrossRef]
[PubMed]
Molecules 2023, 28, 4481 21 of 21

67. Zhang, Y.H.; Li, B.H.; Ma, P.; Zhang, L.M.; Zhang, W.X. An RGH–MOF as a naked eye colorimetric fluorescent sensor for picric
acid recognition. J. Mater. Chem. C 2017, 5, 4661–4669. [CrossRef]
68. Sun, Z.; Sun, J.; Xi, L.; Xie, J.; Wang, X.; Ma, Y.; Li, L. Two Novel Lanthanide Metal–Organic Frameworks: Selective Luminescent
Sensing for Nitrobenzene, Cu2+ , and MnO4 − . Cryst. Growth Des. 2020, 20, 5225–5234. [CrossRef]
69. Zhao, Y.F.; Zeng, H.; Zhu, X.W.; Lu, W.G.; Li, D. Metal–organic frameworks as photoluminescent biosensing platforms: Mecha-
nisms and applications. Chem. Soc. Rev. 2021, 50, 4484–4513. [CrossRef]
70. Ma, W.P.; Yan, B. Lanthanide Functionalized MOF Thin Films as Effective Luminescent Materials and Chemical Sensors for
Ammonia. Dalton Trans. 2020, 49, 15663–15671. [CrossRef]
71. Liu, Y.; Lv, X.; Zhang, X.; Liu, L.; Xie, J.; Chen, Z. Eu(III)-organic complex as recyclable dual-functional luminescent sensor for
simultaneous and quantitative sensing of 2,4,6-trinitrophenol and CrO4 2− in aqueous solution. Spectrochim. Acta A Mol. Biomol.
Spectrosc. 2020, 239, 118497. [CrossRef]

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