PROGRESS REPORT
Fluorescent Sensors
Multicenter Metal–Organic Framework-Based Ratiometric
Fluorescent Sensors
Shuangyan Wu, Hui Min, Wei Shi,* and Peng Cheng*
Dedicated to the 100th anniversary of Nankai University
Metal–organic frameworks (MOFs) with multiple emission centers are newly
emerging as ratiometric sensors owing to their high sensitivity and high
selectivity toward a wide range of targeted functional species. Energy transfer
between the light-absorbing group and emission centers and between different
emission centers is the key to rationally design and synthesize MOF-based
ratiometric sensors. A good match between the energy levels of the light-
absorbing groups and emission centers is the prerequisite for MOF-based
sensors to exhibit multiple emissions, and a good match of the MOF-based
sensors and those of the targeted species can increase the sensitivity and
selectivity, but this match is highly challenging to obtain via synthesis. MOFs
with multiple emission centers can be produced by functionalizing MOFs
with multiple lanthanide centers, organic luminophores, dyes, carbon dots,
and other such emissive groups. In this progress report, recent advances
in the strategies for synthesizing MOFs with multiple emission centers and
their applications for ratiometric sensing of solution conditions, including the
pH value, and ion, organic molecule, and biomolecule concentrations, are
summarized, as are the related sensing mechanisms.
1. Introduction
Metal-organic frameworks (MOFs), as a new class of porous
crystalline materials formed using coordination bonds between
metal nodes and organic linkers, have attracted great interest in
material science due to their facile synthesis routes and diverse
functionalities.[1–5] Their porous nature, functional metal nodes,
and organic linkers endow them with great potentials for gas
storage and separation, catalysis, biomedicine, proton conduc-
tivity, magnetism, luminescence, and other fields.[6–12]
Dr. S. Wu, H. Min, Prof. W. Shi, Prof. P. Cheng
Key Laboratory of Advanced Energy Materials Chemistry (MOE)
College of Chemistry
Nankai University
Tianjin 300071, China
E-mail: shiwei@nankai.edu.cn; pcheng@nankai.edu.cn
Prof. P. Cheng
State Key Laboratory of Elemento-Organic Chemistry
Nankai University
Tianjin 300071, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201805871.
DOI: 10.1002/adma.201805871
Adv. Mater. 2020, 32, 1805871 1805871  (1 of 14)
www.advmat.de
The application of MOFs as sensing
materials is one of their most important
applications. Both metal ions and organic
linkers of MOFs are emission centers if
they are well designed. As luminescent
or fluorescent sensors for specific tar-
geted species, MOFs have the following
advantages: i) the structural and func-
tional diversity and tunability of MOFs
match almost all the types of targeted
species such as cations, anions, organic
molecules, and even nanoparticles[13] via
different host–guest interaction mecha-
nisms;[14] ii) the emission intensities can
correlate well with the concentrations of
the targeted species in practical ranges;
and iii) the preparation of MOF-based
sensors and the equipment to measure
the luminescence intensities are facile,
inexpensive, and easy-to-operate in com-
parison with the methods of gas chroma-
tography mass spectrometry (GC/MS) or
high-performance liquid chromatography
(HPLC), which can provide reliable results but usually require
expensive instruments and the usage of large amounts of
solvents.
For the sensing functions of MOF-based sensors, there are
two ways that the luminescent signals change upon interaction
with a guest species: i) a change in the wavelength of the emis-
sion peaks could be found in transition metal–based MOFs
whose emissions are usually from a charge transfer transition
between metal centers and ligands or intramolecular electron
transfer; and ii) a change in the luminescent intensities could
be monitored without a change in the wavelength, which is usu-
ally found in lanthanide-based MOFs because the f–f electron
transitions of lanthanide centers are not influenced by external
perturbations.[11,12,15] The mechanism behind these lumines-
cence signal changes can be classified as photoelectron transfer
(PET), resonant energy transfer (FRET), or competitive absorp-
tion.[15] A comprehensive understanding of the mechanism in
a practical system is of great importance for the rational design
and synthesis of high-performance MOF-based sensors.
For MOFs with one type of emission center, the mono-
chromatic luminescence/fluorescence signal change is good
enough for the quantitative analysis of the analyte; however, the
sensitivity, selectivity, and detection limit are still not compa-
rable to those of the HPLC or GC/MS techniques mentioned
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

above due to the influence of other external conditions.[15] To

improve the high sensitivity, high selectivity, and low detection Shuangyan Wu was born in
limit of the sensing performance, rational design and synthesis Liaoning, China. She received
of ratiometric sensors based on MOFs with multiple emission her B.Sc. degree in 2012 and
centers has been recently demonstrated as a powerful strategy M.Sc. degree in 2015 from
for solving the problems mentioned above because the self-cali- Zhengzhou University. She
brating or self-referencing mechanism from different but corre- was then admitted to Nankai
lated emission centers can minimize the external influence.[16] University and recently
The self-calibrating ability by comparison of the emission received her Ph.D. degree
intensities from different centers can significantly enhance the under the supervision of Prof.
selectivity and sensitivity if the host (MOF) and guest (analyte) Wei Shi and Prof. Peng Cheng
can be well matched. In addition, ratiometric luminescent or in 2018. Her research interest
fluorescent sensors with strong visible color changes are more focuses on rational design
sensitive and beneficial for the on-site detection by the naked and synthesis of metal-organic frameworks for chemical
eyes. There are also kinds of ratiometric sensors based on non- sensing applications.
MOF materials which were well reviewed, for example, the
nanoscale dual-emitting sensors for temperature[17] and the Wei Shi received his B.Sc.
fluorophores with emissions from two excited-states as ratio- and Ph.D. degrees in 2001
metric sensors,[18] but these types of ratiometric sensors are out and 2006 from Nankai
of the scope of this progress report. University under the supervi-
A comprehensive database of MOF-based sensors in which sion of Prof. Peng Cheng.
they are categorized by their target analytes has been estab- He then joined the faculty at
lished and reviewed recently.[11,12,15,16,19] However, MOF-based Nankai University and was
ratiometric sensors were not included. In this progress report, promoted to full professor
we summarize both the synthetic strategies for MOF-based in 2015. He was a visiting
ratiometric sensors with multiple emission centers and their scholar at the University of
sensing applications for a variety of targeted species, especially California, Berkeley, working
environmental and biotic species. with Prof. Jeffrey R. Long.
His current research interests focus on the synthesis and
property studies of metal-organic frameworks for practical
2. Strategies for the Design and Synthesis applications.
of MOF-Based Ratiometric Sensors
Peng Cheng obtained his B.Sc.,
To rationally design and synthesize MOF-based ratiometric M.Sc., and Ph.D. degrees from
sensors, several strategies have been developed. The introduc- Nankai University in 1985,
tion of dual or multiple emission centers, the construction of 1991, and 1994, respectively.
an effective energy transfer pathway between these centers, and Subsequently, he started his
the optimization of host–guest interactions between MOFs and academic career at the same
analytes are key to realize such applications. In addition, chem- university and was appointed
ically tuning the relative amount of the emission centers, the a full professor in 1996. From
space and distance between the emission centers, and the dis- 1997 to 1999, he worked at
tribution of the emission centers are important in the synthesis Laboratoire de Chimie de
route to improve the sensitivity and reduce detection limit of Coordination du CNRS as
the sensor. Based on the emission centers, MOF-based ratio- a visiting professor and at
metric sensors can be classified into i) MOFs with dual emis- Texas A&M University as a postdoctoral research fellow.
sion (from both the metal center and the organic ligand, or Since 2007, he has been Cheung Kong professor at Nankai
from different metal centers, or from different organic ligands); University, where he currently works on functional coordina-
and ii) MOF-based hybrids that incorporate other types of emis- tion polymers and molecule-based materials.
sion centers such as dyes, carbon dots (CDs), and luminescent
complexes.

Lanthanide ions have similar ionic radii and chemical

2.1. MOFs with Two Emission Centers
Excellent design of organic linkers with appropriate energy
levels and metal centers results in singular MOFs that exhibit
dual emission from bimetallic centers, one metal center with
one organic center or two organic emission centers to function
as ratiometric sensors.
behavior, which is conductive for doping two lanthanide ions
into the same crystallographically equivalent metal positions of
MOFs to result in two emission sources, one at each lanthanide
center.[20–25] Eu3+ and Tb3+ ions form centers that strongly emit
light with red and green color, respectively, that can be detected
by the naked eye and have been widely used for the construc-
tion of luminescence materials.[26] For example, chemically

Adv. Mater. 2020, 32, 1805871 1805871  (2 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 1.  a) 3D framework of [Eu2xTb2(1−x)(FDA)3]. b) The emission spectra of [Eu2xTb2(1−x)(FDA)3] excited at 300 nm and the corresponding images of
their luminescence under a 254 nm UV lamp. c) Simplified diagram of the ligand–metal energy transfer processes of [Eu2xTb2(1−x)(FDA)3] (S0, S1, and
T1 are the ground state, the singlet state, and the triplet state of the ligand, respectively). d) Luminescence images of [Eu0.5Tb1.5(FDA)3] show the lumi-
nescence colors at different volume ratios of the mixtures of glycol and 1,4-dioxane under 254 nm UV light. All panels reproduced with permission.[24]
Copyright 2015, Wiley-VCH.

fine-tuning the Eu3+/Tb3+ ratio of the raw materials in the syn-
thetic process resulted in mixed-lanthanide MOF thermom-
eters, Eu0.0069Tb0.9931-DMBDC and Tb0.9Eu0.1-PIA (H2DMBDC:
2,5-dimethoxy-1,4-benzenedicarboxylate; H2PIA: 5-(pyridin-4-yl)
isophthalic acid), which work over wide temperature ranges
with high accuracy.[20,21] These two Ln-MOFs function as ratio-
metric sensors based on the characteristic emissions from Tb3+
and Eu3+ ions, with the emission of the Eu3+ ion further sensi-
tized by the Tb3+ ion. A series of [Eu2xTb2(1−x)(FDA)3] (H2FDA:
furan-2,5-dicarboxylic acid) systems have been studied as ratio-
metric sensors for organic mixtures.[24] The luminescent color
of [Eu2xTb2(1−x)(FDA)3] can be chemically changed from red
to orange, yellow, and green by varying the ratio of Eu3+/Tb3+
(Figure 1). The strong emissions also suggest that FDA2− is an
efficient antenna for sensitizing both Eu3+ and Tb3+ ions. The
use of a similar strategy resulted in another series of zeolite-
like MOFs (ZMOFs) with mixed Tb3+ and Eu3+ ions;[25] of this
series, Eu0.6059Tb0.3941-ZMOF exhibited excellent selectivity for
lysophosphatidic acid which is a biomarker for ovarian cancer.
Mixtures of lanthanide ions can also be introduced into the
pores of anionic MOFs via ion exchange. A nonluminescent
MOF, Bio-MOF-1, was modified by exchanging Tb3+ and Eu3+
cations into pores of its anionic framework (Figure  2). The
resulting Tb/Eu@bio-MOF-1 material exhibited orange-red
emission due to the mixture of the emissions from both Tb3+
and Eu3+ ions.[27]
Dual emission can be obtained from the metal centers and
organic ligands of lanthanide MOFs if the energy absorbed
by the ligand is partially transferred to the lanthanide center.
A europium-based MOF, [Eu2(L)3(H2O)2(DMF)2]·16H2O (H2L:
1,4-bis(5-carboxy-1H-benzimidazole-2-yl)benzene), showed
dual emission, i.e., emission from both organic linkers and
lanthanide centers.[28] Another europium-based MOF, one with
5-boronoisophthalic acid (5-bop), also showed two emissions
based on the ligand and metal centers.[29] Such dual emission,
emission from the ligand and emission from the Eu3+ ions,
is due to insufficient intermolecular energy transfer from the
ligand to Eu3+ ions.

Adv. Mater. 2020, 32, 1805871 1805871  (3 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 2.  a) Synthesis route for Tb/Eu@bio-MOF-1. b) Schematic diagram for the energy transfer from the triplet state of biphenyl-4,4ʹ-dicarboxylic acid
to Ln3+ ions and the metal-to-metal energy transfer from Tb3+ ion to the Eu3+ ion. Reproduced with permission.[27] Copyright 2016, Elsevier.

The functionalization of transition metal–based MOFs with enhancement.[36] KMnF3:Yb3+/Er3+ was studied as a promising
lanthanide ions is another strategy used to construct ratiometric colorimetric upconversion luminescent nanothermometer that
sensors based on emission from lanthanide centers and ligands. can work in the biological temperature region.[37] This mecha-
The coordinated transition metal ion can modulate the energy nism could be applicable for MOF-based ratiometric sensors
levels of the ligand and hence influence the energy transfer but remains further investigations in the near future.
from the ligand to the lanthanide center. A general strategy has
been developed for making a postsynthetic modification (PSM)
with Eu3+ and Cu2+ ions through coordination bonds with the 2.2. Dyes@MOFs
COOH of a nano-MOF, UiO-66-(COOH)2. The resulting
Eu3+/Cu2+@UiO-66-(COOH)2 complex showed characteristic If luminescent guest species with a wide range of emission
Eu3+ emission and ligand-centered emission that can be used wavelengths can be encapsulated into luminescent MOFs, the
for the ratiometric sensing of hydrogen sulfide.[30] A dual-emit- emission ranges can be expanded and hence become more
ting MOF nanohybrid, Ag+/Eu3+@UiO-66-(COOH)2, was syn- adjustable for targeted species.[38] Luminescent dyes have been
thesized by a similar method for Eu3+/Cu2+@UiO-66-(COOH)2 used as chromophores because of their optical and electronic
and was studied as a ratiometric sensor for the detection of
indoor formaldehyde.[31] Introducing Eu3+ ions to a ZnO-doped
UiO-MOF heterostructure resulted in a novel fluorescent ratio-
metric sensor with emission from both Eu3+ and a ligand for
sensing volatile aldehyde gases in vehicles.[32]
Well-designed luminescent ligands in MOFs also produce
dual emissions if the energy transfer efficiency between the
ligand and metal center is limited due to poor energy level
matching. Using a tautomeric ligand for dual emission is a
very interesting method for the design of ratiometric sensors.
A luminescent 2,1,3-benzothiadiazole-conjugated terphe-
nyldicarboxylate (H2-ostpdc) bridging ligand can exhibit
lactam–lactim tautomerism.[33] This ligand was integrated
into a zirconium MOF of UiO-68-type to form UiO-68-osdm.
The dispersion of UiO-68-osdm in chloroform showed two
distinct luminescence bands that are due to the emissions
from the tautomeric lactam (I) and lactim (II) forms of H2-
ostpdc (Figure  3), respectively. In fact, the mixed-ligand
approach is a general method to introduce dual-emitting
organic moieties and was demonstrated for a Zn-MOF,
[(CH3)2NH2][Zn(BTB)2/3(ATZ)]·H2O·DMF (BTB: 1,3,5-tris(4-
carboxyphenyl)-benzene; ATZ: 5-amino-1-H-tetrazolate), to
show dual emission from two separated and competitive
excited states of mixed organic lumophores in thermal equilib-
rium using the Dexter energy transfer (DET) process.[34]
Recently, the discovery of thermally coupled levels in lan-
thanide compounds has led to a new type of ratiometric
temperature sensors.[35] The Yb3+/Eu3+ co-doped NaGdF4 nano­
Figure 3.  Two typical tautomeric forms of the linker ostpdc and the typ-
particle was studied as a representative to demonstrate that the ical resonance electron delocalization of the deprotonated form in the
energy migration-induced surface quenching could be sup- MOF UiO-68-osdm. Reproduced with permission.[33] Copyright 2017,
pressed by increasing temperature, resulting in a fluorescence American Chemical Society.

Adv. Mater. 2020, 32, 1805871 1805871  (4 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 4.  a) Crystal structure of ZJU-88 along the c crystallographic axis: Eu, blue polyhedra; C, gray; O red; H atoms and solvent molecules are omitted for
clarity. b) The dual-emitting ZJU-88⊃perylene composite (EnT: energy transfer; Em: emission). Reproduced with permission.[45] Copyright 2015, Wiley-VCH.
properties.[39,40] The construction of luminescent dye/MOF
hybrids for ratiometric sensors is desired.
Ionic dyes can be exchanged with the counterions in
the cationic frameworks of MOFs. A luminescent MOF,
[(CH3)2NH2]2[(Zn2O)L]·5DMF (NENU-519), has been synthe-
sized with tetrakis[4-(carboxyphenyl)oxamethyl]methane acid
(H4L).[41] The anionic framework can selectively absorb cationic
dyes based on ionic interactions rather than the size-exclusion
effect to give Rh6G@NENU-519 (Rh6G: rhodamine 6G) as a
dual-emission sensor for benzene derivatives. Rh6G has also
been encapsulated into the pores of {(NH2Me2)[Zn3(µ3-OH)(tpt)
(TZB)3](DMF)12}n (tpt: 2,4,6-tri(4-pyridyl)-1,3,5-triazine; H2TZB:
4-(1H-tetrazol-5-yl)benzoic acid),[42] which exhibits red emission
from Rh6G and blue emission from the ligand.
Neutral dyes have also been introduced into MOFs by
exchanging with neutral molecules in the pores. A Cd-MOF
(CZJ-3) was synthesized and further used to absorb rhodamine
B (RhoB) to form RhoB@CZJ-3.[43] RhoB was also introduced
into the framework of a Zn-MOF ([Zn2(oba)2(4-bpdb)]n·2DMF;
H2oba: 4,4-oxybisbenzoic acid; 4-bpdb: 1,4-bis(4-pyridyl)-2,3-
diaza-1,3-butadiene).[44] These two RhoB/MOF hybrids showed
emission from both the ligands and RhoB.
In addition to the dye/transition-metal MOF hybrids, the
incorporation of dyes into lanthanide MOFs is desired for ratio-
metric sensors because the energy transfer process between
dyes and MOFs can be finely tuned through the spectral overlap
between dyes and lanthanide MOFs. The organic dye of perylene
was incorporated into a Ln-MOF (ZJU-88) to form the composite
of ZJU-88⊃perylene (Figure  4).[45] ZJU-88⊃perylene showed
a red emission at 615 nm from Eu3+ ions and a blue emis-
sion at 473 nm from perylene. An amino group–rich Eu-MOF
([Eu(atpt)1.5(phen)(H2O)]; H2atpt: 2-aminoterephthalic acid; phen:
1,10-phenanthroline) with the high quantum yield of 48% was
modified covalently with methyl red (MR) to yield MR@Eu-MOF,
which showed emissions from both MR and Eu3+ ions.[46]
2.3. Carbon Dots@MOFs
Carbon dots, as a new class of luminescent nanoparticles with fas-
cinating properties such as high photoluminescence stability,[47]
Adv. Mater. 2020, 32, 1805871
www.advmat.de
green and facile synthesis,[48] low toxicity,[49] good biocompat-
ibility,[50] good water solubility,[51] and selectivity for analytes,[52]
have attracted increasing interest as luminescent materials.[53,54]
Recently, a strategy for incorporating CDs into MOFs was devel-
oped for the construction of ratiometric sensors.[55,56]
Strongly blue light-emitting nitrogen and sulfur-codoped
CDs (N,S-CDs) encapsulated in the framework of a red-emitting
Eu-MOF ([Ln(btc)(H2O)]·guest; H3btc: 1,3,5-benzenetricarbox-
ylic acid) was synthesized with a one-pot method, with N,S-CDs
added to the precursors of this Eu-MOF.[57] An Al-based MOF
(MOF-253) was functionalized with CDs and Eu3+ ions to show
not only emissions from both the CDs and Eu3+ ions but also
high water stability, which is important for detecting targeted spe-
cies in water such as Hg2+.[58] Red p-phenylenediamine-derived
“p-CDs” were encapsulated into an In-MOF. The Tb3+ ion was
further introduced to this p-CD/MOF hybrid to give a dual-emit-
ting hybrid, Tb3+@p-CD/MOF, that acts as a ratiometric sensor
for the detection of water molecule in organic solvents.[59]
2.4. Luminescent Complexes@MOFs
Luminescent complexes such as [(Ru(bpy)3]2+ and
[Ir(CF3-ppyF2)2(bpy)]+ (bpy: bipyridine; CF3-ppyF2:
5-(trifluoromethyl)-2-(2,4-difluorophenyl)pyridine) have stable
red and green emissions, respectively, in water and organic
solvents. Their high chemical and photostability make them
popular as ideal luminescent centers.[60,61] A facile strategy
of encapsulating red-emitting [Ru(bpy)3]2+ in the pores of
MIL-101(Al)-NH2 with blue emissions via one-pot synthesis
resulted in a ratiometric fluorescent sensor, Ru@MIL-NH2,
that detects water in organic solvents in real time.[62] Recently,
a novel trichromatic MOF composite was obtained by incorpo-
rating specific amounts of green-emitting [Ir(CF3-ppyF2)2(bpy)]+
and red-emitting [Ru(bpy)3]2+ into a blue-emitting Zn-MOF.[63]
The anionic framework of the Zn-MOF with large pores ena-
bles the inclusion of complex cations. The white-light emission
was achieved by tuning the molar ratios between the emission
centers. Another interesting example of Eu3+@UMOFs was
reported by Yan et al. This material displayed fluorescent emis-
sions at 485, 530, and 614 nm, which has a recognition ability
1805871  (5 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
for Hg2+, Ag+, and S2−. Logic system performing multiplexed
analysis of the two or three ions in solution was further realized
using this material.[64] Additionally, encapsulating fluorescein
isothiocyanate and Eu complex–functionalized Fe3O4 into a
zeolitic imidazolate framework (ZIF-8) resulted in a core–shell-
like nanoprobe that exhibited emission from the Eu complex
and FITC.[65]
3. MOF-Based Ratiometric Sensors for Various
Applications
MOFs with multiple emission centers are a rapidly growing
class of ratiometric sensors for quantifying many functional
species. Different emission centers can have different lumines-
cence/fluorescence responses to the targeted species based on
specific interactions between MOFs and the targeted species.
In comparison to the single-response sensors and based on the
relative ratio of the emission intensities, ratiometric sensors
have shown increased accuracy and sensitivity and selectivity
for the targeted species if the MOF-based sensors and guest
species are well matched because many nonanalyte factors can
be excluded. Selected ratiometric fluorescent sensors based on
MOFs have been summarized in Table 1.
3.1. Water and Humidity Sensors
Water is a universal molecule that influences almost all the con-
ditions related to human life. The development of facile, rapid,
and selective water-sensing methods is of significant impor-
tance in various areas such as chemical industrial processes,
environmental monitoring, pharmaceutical processes, and
food inspection.[66,67] The nanohybrid material Eu-MOF/N,S-
CDs were studied as a ratiometric sensor for water.[57] When
Eu-MOF/N,S-CDs were dispersed in water, the encapsulated
N,S-CDs were released and strongly emitted blue light, while
the red emission of the Eu-MOFs was quenched by O–H oscil-
lators. Based on the unique luminescent properties of the Eu-
MOF/N,S-CDs, a sensitive and visual ratiometric sensor for
the detection of water in ethanol has been developed, and it
exhibits a response range of 0.05–4% and a detection limit of
0.03%.
A hybrid material (Tb3+@p-CDs/MOF) with dual emission
originating from green-emitting Tb3+ and red-emitting p-CDs
responded differently to water content in organic solvents than
the above example because the p-CDs are prone to aggrega-
tion in water (Figure 5).[59] As a result, this hybrid showed dif-
ferent emissions in water and organic solvents, which can be
used as ratiometric sensor for the detection of water content in
organic solvents. Moreover, relative humidity (RH) can also be
determined by this ratiometric sensor, with a working range of
33.0–85.1% in the atmosphere.
A ratiometric sensor based on Ru@MIL-53(Al)-NH2 was
studied for real-time and high-sensitivity determination of water
content in organic solvents. The protonation of the nitrogen
atom in MIL-53(Al)-NH2 changed the emission behavior of
MIL-53(Al)-NH2, and [Ru(bpy)3]2+ maintained red emission as
a reference. High sensitivity, a low detection limit of 0.02% v/v,
Adv. Mater. 2020, 32, 1805871 1805871  (6 of 14)
www.advmat.de
a wide response range of 0–100%, and a fast response in less
than 1 min are achieved with this ratiometric sensor.[63]
A luminescent sensor based on {[Eu2(L)3(H2O)2
(DMF)2]·16H2O}n (H2L: 1,4-bis(5-carboxy-1H-benzimida-
zole-2-yl)benzene), with an open channel filled with water
molecules, was studied for determining the RH.[28] The frame-
works remain stable under relatively high humidity, which was
attributed to water structures in the pores preventing solution
water molecules to approach and break the EuO bonds. The
Eu-MOF serves as a ratiometric sensor with dual emission for
RH in the range of 33.0–85.1% based on the ratio of the lumi-
nescence intensities of the ligand and the characteristic emis-
sion of Eu3+ ions.
A mixed-lanthanide version of PCM-22 with triphenylphos-
phine was applied for the detection of trace amounts of H2O
in D2O.[68] Taking advantage of the two emissions, one of Eu3+
(616 nm) and one of Tb3+ (543 nm), Eu1:Tb5-PCM-22 showed
extraordinary ability to detect H2O in D2O at concentrations
between 10 and 100 ppm. The change in I543/I616 is ascribed
to OH2/OD2 exchange, with the less effective Eu3+ excited-state
quencher of the O–D oscillator.
3.2. pH Sensors
The pH value is significant for a wide range of chemical
and biochemical reactions. MOFs exhibiting pH-dependent
fluorescence responses, especially in the biologically inter-
esting range of pH 5–7.5, are potential candidates for pH
sensors in aqueous solution or in living cells.[69–71] An excep-
tional acidic and alkaline stable (pH range 2.0–12.2) MOF,
[Cd1.5(EDDA)]·(H3O)·3H2O (Cd-EDDA, H4EDDA: 5,5ʹ-(ethane-
1,2-diylbis(oxy))diisophthalic acid), showed an excellent ratio-
metric pH response in the range of pH from 2.0 to 11.5.[72]
Detailed mechanistic studies demonstrated that the sensing
property was due to the hydrogen bond formation between the
oxygen atoms of the ether bond of the framework and hydro-
chloric acid/hydroxide. Cd-EDDA is the first example of an
MOF-based ratiometric sensor for pH and can easily be regen-
erated by modulation of the solution pH.
A series of nanoscale Ln-MOFs of the form
Eu2xTb2−2x(fum)2(ox)(H2O)4 (EuxTb1−x-NMOF, x  = 0.016, 0.034,
0.056, and 0.084) was synthesized. Eu0.034Tb0.966-NMOF showed
a self-calibrating pH-sensing luminescence based on pH-
dependent emissions from Eu3+ and Tb3+ ions.[73] Eu0.034Tb0.966-
NMOF also exhibited high water stability and emission from both
Eu3+ and Tb3+ ions, allowing accurate and reliable sensing of pH
values from 3 to 7. Its low cytotoxicity and good biocompatibility
were demonstrated by the MTT assay, and an optical microscopy
assay indicated its potential for physiological pH sensing.
Ratiometric sensing can be realized by changing the coor-
dination geometries of the lanthanide centers in MOFs. For
a single emitting center, for example, Eu3+, the luminescence
can differ if the conditions surrounding the Eu3+ ions differ.
PSM of nanoscale MOF-253 with Eu3+ ions and subsequent
treatment with TTA (TTA: 2-thenoyltrifluoroacetone) gener-
ated MOF-253-Eu-TTA.[74] Two types of Eu3+ units, with dif-
ferent coordination environments, were obtained by tuning
the ratio of Eu3+/deprotonated TTA, where Eu1 was linked to
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Table 1.  Selected ratiometric fluorescent sensors based on MOFs.

Compounds Analyte Working range LOD Ref.

{[Eu2(L)3·(H2O)2·(DMF)2]·16H2O}n Humidity 33.0–85.1% – [28]
Tb3+@p-CDs/MOF Humidity 33.0–85.1% 0.28% [59]
Ru@MIL-101(Al)-NH2 H2O 0–1 0.02% [62]
Eu-MOF/N,S-CDs H2O 0.05–4 % 0.03% [57]
[Mg(H2dhtp)(H2O)2]·DMA H2O 0.05–5% – [67]
Eu1:Tb5-PCM-22 H2O 10–120 000 ppm – [68]
1
[Eu2(L )3(H2O)4]·3DMF DMF – – [90]
{[Cd1.5(EDDA)]·(H3O)(H2O)3}n pH 2.0–11.5 – [72]
Eu0.034Tb0.966-NMOF pH 3.0–7.0 – [73]
MOF-253-Eu-TTA pH 5.0–7.2 – [74]
[(CH3)2NH2]2[(Zn2O)L]·5DMF VOM – – [41]
Rho@[Cd(L2)(H2O)]·4DMF·2H2O VOM – – [43]
(Me2NH2) [Zn2(L3)(H2O)]·4DMA VOM – – [63]
Eu0.47Tb0.53-CTP-COOH Fe3+/VOCs – – [75]
Carbon dots Fe3+ – – [47]
BPEI-CQDs Cu2+ 10–1100 × 10−9 m 6 × 10−9 m [52]
−9
BPEI-CQDs Cu2+ 2–1000 × 10 m – [55]
NPs@MOFs Cu2+ 0.1–1 × 10−9 m 0.1 × 10−9 m [65]
g-C3N4 Cu2+ 0–10 × 10−6 m 0.5 × 10−9 m [76]
−6
Eu3+ /CDs@MOF-253 Hg 2+
0.065–150 × 10 m 13 ppb [58]
Eu2(5-bop)3(H2O)2 F− 4–80 × 10−6 m 2 × 10−6 m [29]
MIL-125(Ti)-NH2-Eu 3− – – [82]
PO4
C2O42− – –
Eu3+/Cu2+@UiO-66-(COOH)2 Hydrogen sulfide 0–625 × 10−6 m 5.45 × 10−6 m [30]
−3 −6
Tb3+@Cu-MOF Hydrogen sulfide 0–1.6 × 10 m 1.20 × 10 m [88]
Eu3+/Ag+@UIO Nano-MOF Formaldehyde 0–1 ppm 51 ppb [31]
Eu3+@ZUM Formaldehyde 0–5 ppm 42 ppb [32]
{(NH2Me2)0.9(Rh6G)0.1[Zn3(OH)(tpt)(TZB)3]·(DMF)11}n 2,4,6-Trinitrophenol – – [42]
RhB@[Zn2(oba)2(4-bpdb)]n·2DMF 4-Nitroaniline – – [44]
Eu0.5Tb1.5(FDA)3 V1,4-dioxane/V 0–1 – [24]
UiO-68-osdm Diethylamine 1–10 × 10−6 m 1.3 × 10−9 m [33]
Carbon dots Cancer cell – – [50]
MR@EuMOFs Histamine 0–250 × 10−6 m 0.1 × 10−6 m [46]
CDs@ZIF-8 Quercetin 0.01–50.0 × 10−6 m 3.5 × 10−9 m [56]
Mixed-crystal Ln-MOF Coumarin 1–100 × 10−6 m 2.3 × 10−6 m [95]
Caffeine 1–100 × 10−6 m –
Ag+@Eu complex Aspartic acid 0–1000 × 10−6 m 0.46 × 10−6 m [97]
Eu0.6059Tb0.3941-ZMOF Lysophosphatidic acid 1.4–43.3 × 10−6 m – [25]
Tb/Eu@bio-MOF-1 Dipicolinic acid – 34 × 10−9 m [27]
Tb/Eu(BTC) Dipicolinic acid 50–700 × 10−9 m 4.55 × 10−9 m [93]
RGH-MOF Picric acid 2–200 × 10−6 m 0.45 × 10−6 m [91]
MPA-CdTe QDs@NH2-MIL-53(Al) 6-Mercaptopurine 0–50 × 10−6 m 0.15 × 10−6 m [94]

LOD: limit of detection; VOM: volatile organic molecules; H4dhtp: 2,5-dihydroxy-terepthalic acid; PCM: phosphine coordination materials; L1: 2ʹ,5ʹ-bis(methoxymethyl)-
[1,1ʹ:4ʹ,1″-terphenyl]-4,4″-dicarboxylate; H2L2: (E)-4-(2-carboxyvinyl)benzoic acid; H5L3: 2,5-(6-(3-carboxyphenylamino)-1,3,5-triazine-2,4-diyl-diimino)diterephthalic acid;
CTP-COOH: hexa-(4-carboxyl-phenoxy)-cyclotriphosphazene; BPEI: branched poly-(ethylenimine); NPs: nanoparticles; ZUM: ZnO@Uio-MOF; bio-MOF-1: Zn8(Ad)4
(BPDC)6O·2Me2NH2; Ad: adeninate; H2BPDC: biphenyldicarboxylate.

Adv. Mater. 2020, 32, 1805871 1805871  (7 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 5. Mechanism of the luminescence response of Tb3+@p-CDs/
MOF toward water in organic solvents. Reproduced with permission.[59]
Copyright 2017, Royal Society of Chemistry.
bipyridine and Eu2 was linked to both bipyridine and deproto-
nated TTA (Figure 6); hence, Eu1 and Eu2 have different excita-
tion wavelengths, 330 and 375 nm. MOF-253-Eu-TTA showed
a self-calibrating property for pH sensing, with the fluores-
cence intensities of only one of the two types of Eu3+ being pH
dependent. The sensor showed a linear fluorescent response in
the pH range of 5.0–7.2, which is suitable for working with bio-
logical fluids such as blood and cell culture media.
3.3. Ion Sensors
Sensing for biological or environment-related ions is important
for their potential applications in medicine, chemical engineering
and environments.[75,76] For example, Cu2+ ion is a biological
trace element for organisms. Overdose of Cu2+ ion always leads
to many diseases in humans,[77,78] and hence it is important
to quantify Cu2+ ion with facile method such as luminescent
sensing. A dual-emitting MOF-based sensor was synthesized
by encapsulating FITC and Eu-functionalized Fe3O4 into ZIF-8,
a well-known MOF, for ultrasensitive detection of Cu2+.[65] FITC
was treated as a reference and limited the influence from external
uncertainties. The signal of Eu-functionalized Fe3O4 is quenched
by Cu2+. The porous ZIF-8, working as a protective layer, not only
prevents the aggregation of nanoparticles but also enriches the
target analytes to enhance the sensing ability. The linear response
range was (0–40) × 10−6 m for Cu2+, and the detection limit of the
Figure 6.  Schematic diagram of MOF-253 modified by Eu3+ complexes with TTA. Reproduced with permission.[74] Copyright 2014, Royal Society of
Chemistry.
Adv. Mater. 2020, 32, 1805871 1805871  (8 of 14)
www.advmat.de
Figure 7. Schematic of the F− detection mechanism and luminescent
spectra upon the addition of F−. The inset is the photographs of the
mixture to show the color and intensity at different concentrations of
F−. Reproduced with permission.[29] Copyright 2017, American Chemical
Society.
sensor was 0.1 × 10−9 m, which is 20 000 times lower than the
maximum concentration of allowable Cu2+ in drinking water. In
addition, this sensor was also demonstrated for the ratiometric
fluorescence imaging of Cu2+ ions in live cells.
Hg2+ is one of the most toxic metal ions that harms human
health and the environment; hence, the development of facile
methods for the detection of Hg2+ ions is an urgent chal-
lenge.[79,80] The encapsulation of optical active CDs and Eu3+ into
MOF-253(Al) generated Eu3+/CDs@MOF-253, which can func-
tion as a ratiometric sensor for Hg2+.[58] The relative ratios of flu-
orescence intensities (IEu/ICD) linearly respond to Hg2+ concen-
trations in the range of (0.065–150) × 10−3 m with a 13 × 10−9 m
detection limit. The quenching of CDs by Hg2+ was due to the
coordination between Hg2+ and the functional groups of CDs.
In addition to cations, toxic anion pollutants have also
attracted attention for their serious threat to human health
and the environment.[81] A dual-emission Eu-MOF-based rati-
ometric sensor for F− was synthesized with a boric acid func-
tional group. Boric acid can be used to specifically identify F− in
an accessible site. Tuning the energy transfer efficiency between
5-boronoisophthalic acid and Eu3+ ion is responsible for the rati-
ometric sensing behavior. This sensor displayed a wide linear
response range of (0.065–150) × 10−3 m with high selectivity and
a low detection limit of 2 × 10−6 m (Figure 7).[29] An orthogonal
readout pattern based on luminescence intensity and quantum
yield of the dual-emitting Eu3+-doped MOF MIL-125(Ti)-AM-Eu
was studied as a function of different anions such as PO43− and
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

C2O42−,[82] which displayed a one-to-one correspondence to the
concentration of the accommodated anions.
3.4. Volatile Organic Compounds (VOCs) and Gas Sensors
VOCs are a new type of organic pollutant and have high vapor
pressure at room temperature due to their low boiling point;
thus, they easily evaporate from the liquid phase into air and
are very harmful to human health. Detection of VOCs by flu-
orescence/luminescence-sensing methods is highly desired
because of the facile preparation, fast response and low cost
of these assays. A “bimetallic-luminescent center” strategy for
color-gradient luminescence sensing of dioxane in glycol at a
large volume-ratio range was developed recently.[24] The dis-
tinct emission behavior in the bimetallic lanthanide MOF
[Eu0.5Tb1.5(FDA)3] as a function of the dioxane/glycol volume
ratio is due to the influence of the targeted compounds on the
energy transmission from Tb3+ to Eu3+.
Among VOCs, benzene and its derivatives are substantively
toxic air/water pollutants.[83,84] A RhoB@Cd-MOF (RhoB@
CZJ-3) sensor was designed and synthesized to show emissions
from both the ligand and RhoB. Excellent correlation between
the VOC concentration and the ratios of ligand/dye emission
intensities was achieved.[43] This RhoB@CZJ-3 sensor is stable,
instantaneous and self-calibrating, rendering it promising for
practical applications. Very recently, a white light–emitting
trichromatic MOF composite was designed, synthesized and
applied as a multidimensional ratiometric sensor for VOCs
(Figure  8a).[63] VOC-dependent relative fluorescent intensity
changes can be correlated to a 2D identification code and work
well for quantification of VOCs, even for very similar aromatic
molecules such as xylenes, benzene, and toluene (Figure 8b,c).
Formaldehyde is a serious indoor air pollution.[85] A dual-emit-
ting MOF nanohybrid of Ag+/Eu3+@UiO-66 was developed for
the detection of formaldehyde indoors.[31] Formaldehyde interacts
with Ag+ and hence causes an opposite luminescence response
of the sensor. The linear response range was 0–1 ppm for formal-
dehyde, and a detection limit of 51 ppb was obtained by the ratio-
metric sensor with a fast response. To increase the selectivity for
formaldehyde over other aldehydes, a dual-emitting sensor was
synthesized by introducing Eu3+ to ZnO-doped UiO-MOF het-
erostructures.[32] When this sensor was studied with aldehyde gas
targets, it showed excellent selectivity and sensitivity, with a detec-
tion limit of 42 ppb for formaldehyde, 58 ppb for acetaldehyde
and 66 ppb for acraldehyde at room temperature. This sensor
can also work for aldehydes in the temperature range from 25 to
65 °C. A mechanistic study showed that reducing the number of
aldehyde molecules contributed to charge transfer from ZnO to
Eu3+ for increasing the emission intensity at 614 nm from Eu3+
and hence benefit for the selectivity.
Hydrogen sulfide, as an intriguing endogenous signaling
molecule, is associated with various physiological and patho-
logical processes.[86,87] The detection of H2S has become a long-
term and crucial task for better understanding the role of H2S in
biological systems. A general logic gate strategy for luminescent

Figure 8.  a) The framework of the trichromatic MOF; the yellow crosses outline the shapes of the channels. b) The 2D decoded map of ten solvent
molecules, based on two emission intensity ratios: IMOF/I[Ir]+ and IMOF/I[Ru]2+. c) The 2D decoded map of seven similar aromatic molecules, based on
two emission intensity ratios: IMOF/I[Ir]+ and IMOF/I[Ru]2+. d) The 3D ratiometric sensing of the VOCs when time is added as the third dimension (the
overlapped data points from the 12 VOC vapors without quenching effects are combined to form a column). All panels reproduced with permission.[63]
Copyright 2018, Royal Society of Chemistry.

Adv. Mater. 2020, 32, 1805871 1805871  (9 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
turn-on and ratiometric sensing of H2S was developed based
on the PSM of UiO-66-(COOH)2 with Cu2+ and Eu3+ ions.[30]
This ratiometric sensor showed high sensitivity and high selec-
tivity for H2S because H2S is chemical affinity for Cu2+ in the
system and hence strongly enhances the fluorescence of Eu3+
and quenches the broad ligand emission. The linear response
range was as high as 625 × 10−6 m, with a low detection limit of
5.45 × 10−6 m. PSM of an MOF [Cu(HCPOC)2]n (Cu1, H2CPOC:
5-(4′-carboxyphenoxy)nicotinic acid) generated the H2S turn-on
ratiometric sensor Tb3+@Cu1.[88] As a strong electron donor,
H2S strongly enhances the luminescence of Tb3+ through its
superior affinity for Cu2+ ions, and as a result the sensor showed
high sensitivity and selectivity with a linear response range up
to 1.6 × 10−3 m and a low detection limit of 1.20 × 10−6 m.
3.5. Nitroaromatic Explosive Sensors
Explosive molecules have been used in a wide range of industrial
roles such as dyes, fireworks, antiseptics, and pharmaceuticals.[89]
These chemicals are highly poisonous and difficult to degrade
in nature and thus have induced serious health and environ-
mental issues.[90] Facile, fast and selective detection of explosive
molecules is highly important, and ratiometric sensors based on
MOFs with multiple emissions are highly desired.
An anionic MOF {(NH2Me2)[Zn3(µ3-OH)(tpt)(TZB)3]
(DMF)12}n was modified by the encapsulation of Rh6G to form
a ratiometric sensor that exhibits blue emission from the ligand
and red emission from Rh6G.[42] This sensor can rapidly detect
trace amounts of 2,4,6-trinitrophenol (TNP) in the presence
of other competitive nitroaromatic molecules, due to the self-
calibrating mechanism. Immobilizing Rh6G hydrazide (RGH)
onto the surface of the Ln-MOF (Eu(BTC)) (H3BTC: 1,3,5-ben-
zenetricarboxylic acid) generated a ratiometric fluorescent
sensor.[91] In the presence of TNP, the red emission of Eu3+ was
quenched by donor–acceptor electron transfer, and green emis-
sion from RGH was increased by the spirolactam ring-opening
of rhodamine. This RGH@Eu(BTC) sensor showed high selec-
tivity for picric acid among nitroaromatic compounds and
could be used with the naked eye. The linear response range is
(2–200) × 10−3 m, and the detection limit is 0.45 × 10−3 m.
The trichromatic MOF composite with white light–emitting
was also studied for nitroaromatic explosives. Importantly, when it
was exposed to selected nitroaromatic vapors the time-dependent
evolution of the two ratios can be mapped to achieve the first 3D
identification code for these compounds (Figure 8d).[63]
3.6. Biomarker Sensors
The term biomarker refers to a measurable indicator of a spe-
cific biological state or condition that can be used for exam-
ining biological, pathogenic, or pharmacologic responses. For
example, as biomarker for ovarian cancer and other gynecologic
cancers, lysophosphatidic acid (LPA) is important for early
therapy of its related cancers.[92] A series of isostructural zeolite-
like Ln-MOFs with different molar ratio of Tb3+ to Eu3+ in the
nodes was designed and synthesized.[25] A methanol suspen-
sion of MZMOF-3, a property-optimized Ln-MOF, exhibited
Adv. Mater. 2020, 32, 1805871 1805871  (10 of 14)
www.advmat.de
highly selective detection for LPA. A linear correlation between
the relative luminescence intensity and the concentration of
LPA was obtained and enable quantitatively sensing LPA in
physiologically relevant range of (1.4–43.3) × 10−6 m (Figure 9).
This ratiometric sensor showed high sensitivity and selectivity
for LPA, even in the presence of major components of blood
plasma, due to its self-calibrating mechanism.
A rapid, facile, highly selective and sensitive ratiometric
sensor was synthesized by cation exchange of Eu3+ and Tb3+
into a biocompatible anionic bio-MOF-1. For this sensor, the
Tb3+ emission of this sensor can be enhanced by dipicolinic
acid (DPA) through the energy transfer from ligand to metal,
and the emission of Eu3+ was quenched by the interruption of
energy transfer from Tb3+ to Eu3+, resulting in highly sensitive
and selective detection of DPA, which is an anthrax biomarker.
The working range is from 50 to 700 × 10−9 m and the detec-
tion limit is 4.55 × 10−9 m.[27] Another ratiometric sensor for the
rapid detection and naked-eye recognition of DPA using nano-
sized bimetallic MOF Tb/Eu(BTC) was reported.[93] The various
responses of Tb3+ and Eu3+ to DPA are due to the modulation of
energy transfer processes of this sensor because DPA can coordi-
nate with Tb3+ by exchanging the coordinated water that results
in the enhancement of the green luminescence of Tb3+. The
ability of this sensor to work in human serum was also studied.
6-Mercaptopurine (6-MP) is an anticancer drug but it has
serious side effects. A ratiometric luminescent sensor for the
selective detection of 6-MP was synthesized by the hybridiza-
tion of the blue-emitting NH2-MIL-53(Al) with green-emitting
quantum dots of 3-mercaptopropionic acid-capped CdTe (MPA-
CdTe QDs).[94] The luminescence of NH2-MIL-53(Al) of the
sensor was selectively quenched upon addition of 6-MP due to
strong inner filter effects, but the luminescence of the MPA-
CdTe QDs was enhanced. As a result, the ratiometric sensor
exhibited high selectivity and selectivity toward 6-MP in the
range of (0–50) × 10−6 m and the detection limit is 0.15 × 10−6 m.
Early detection of food spoilage is of high importance for
human health and economics. Biogenic amines such as hista-
mine (HI) are indicators for food spoilage. A facile and effec-
tive route to combine a fluorescent sensor of MR@EuMOF
and one-to-two logic operation was designed for testing for
food spoilage.[46] Double-responsive fluorescence was achieved
via energy transfer from the ligands to both MR and Eu3+. Port-
able sensors based on MR@EuMOF hydrogels were also syn-
thesized, and they exhibited a color change in the presence of
HI. Moreover, an advanced one-to-two logic gate sensing device
was constructed using the concentration of HI as the input
and dual emissions as the output, allowing the direct and real-
time analysis of HI for food freshness evaluations (Figure 10).
Isostructural mixed-crystal Ln-MOFs were synthesized by
changing the molar ratio of Tb3+ to Eu3+; in which Eu0.1Tb0.9-
BTC was selected for the preparation of a luminescent Ln-MOF
thin film.[95] The emission intensity at 619 nm (Eu3+, 5D0 → 7F2)
relative to that at 547 nm (Tb3+, 5D4  → 7F5) strongly depends
on the guest pharmaceutical molecules and hence enables this
ratiometric sensor to show fingerprint correlation between
different concentrations of selected pharmaceutical molecules
and the emission intensity ratios.
Aspartic acid, as a common amino acid, is important in bio-
logical activities for its role in the central nervous system as an
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 9.  a) Crystal structure of Tb-ZMOF. b) Tiling representation of the rho topology of Tb-ZMOF. c) Relative luminescence intensity changes of
MZMOF-3 in the presence of different analytes. d) Integrated luminescent intensity of MZMOF-3 suspended in MeOH with LPA. All panels reproduced
with permission.[25] Copyright 2015, American Chemical Society.

excitatory neurotransmitter.[96] By the introduction of Eu3+ and
Ag+ to bio-MOF-1 via an in situ synthetic process followed by a
postsynthetic method, a Ag+@Eu-complex hybrid system was
constructed and studied as a ratiometric sensor for aspartic
acid.[97] The energy transfer between aspartic acid and the
hybrid influenced the energy transfer process between Eu3+
and the ligand, which enhanced the emission from the ligand
and decreased the emission from Eu3+. In addition, the release
of H+ from aspartic acid is also responsible for the sensing
function. This ratiometric sensor showed high selectivity for
aspartic acid among 19 other common amino acids, and the
detection limit is 0.46 × 10−6 m.
4. Conclusions and Outlook
Recent research progress on MOFs with dual or multiple emis-
sion centers for application as ratiometric sensors has been
summarized. The presence of multiple emission centers in
MOFs can endow the sensors with a self-calibrating function
without influence from external stimuli and hence enhance
selectivity and sensitivity. The main synthetic methods used for
the functionalization of MOFs so that they serve as ratiometric
sensors include the construction of singular MOFs with dual
emission, metal doping of MOFs, and luminophore (dyes,
CDs, etc.) encapsulation. These functionalized MOFs have
been applied well as ratiometric sensors for various functional
species such as water, ions, volatile organic chemicals, explo-
sives, and biomolecules.
However, compared to studies on single-emitting MOF-
based sensors, MOF-based ratiometric sensors with multiple
centers are still in their early stage and have the following chal-
lenges: i) the water stability of the MOF-based sensors needs to
be further enhanced because water is the main component in
environmental and biological media. High water stability can
endow sensors with high recyclability and render them inex-
pensive. ii) The synthesis of luminophore-encapsulated MOFs
is relatively complicated; controlling the content of lumino-
phores in MOFs is hence challenging, but it is important for
ratiometric sensing functions. iii) The detection limit for the
targeted species needs to be further improved or well matched
with the range of practical systems. iv) The sensors should
work in practical or complicated systems, requiring the sensors
to be studied under real-time conditions (temperature, pres-
sure, etc.) at various concentrations of both analytes and inter-
fering species. v) The basic principles involved in the sensing

Adv. Mater. 2020, 32, 1805871 1805871  (11 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 10.  a,c) Column diagrams of the normalized luminescence intensities of FMR and FEu as a function of HI at concentrations of a) 250 × 10−6  m
and c) (0–100) × 10−6 m. b,d) Truth tables for b) the one-to-two decoder logic gate and d) the logic analytical device for HI. All panels reproduced with
permission.[46] Copyright 2017, Wiley-VCH.

mechanisms, in terms of the interaction between MOF hosts [1] H. Furukawa, K. E. Cordova, M. O’Keeffe, O. M. Yaghi, Science 2013,
and the targeted species, are still vague, known only qualita- 341, 1230444.
[2] J. R. Long, O. M. Yaghi, Chem. Soc. Rev. 2009, 38, 1213.
tively, and thus require further quantitative investigations com-
[3] H. C. Zhou, J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112,
bined with theoretical calculations.
673.
[4] H. C. Zhou, S. Kitagawa, Chem. Soc. Rev. 2014, 43, 5415.
[5] G. Maurin, C. Serre, A. Cooper, G. Férey, Chem. Soc. Rev. 2017, 46,
Acknowledgements 3104.
[6] Y. B. He, W. Zhou, G. D. Qian, B. L. Chen, Chem. Soc. Rev. 2014,
S.W. and H.M. contributed equally to this work. This work was 43, 5657.
supported by the National Natural Science Foundation of China (Grant [7] J. W. Liu, L. F. Chen, H. Cui, J. Y. Zhang, L. Zhang, C. Y. Su, Chem.
Nos. 21622105 and 21861130354), the Natural Science Foundation of Soc. Rev. 2014, 43, 6011.
Tianjin (Grant No. 18JCJQJC47200), the Ministry of Education of China [8] P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P. Couvreur,
(Grant No. B12015), and the Royal Society (Grant No. NAF\R1\180297).
G. Férey, R. E. Morris, C. Serre, Chem. Rev. 2012, 112, 1232.
[9] X. Meng, H.-N. Wang, S.-Y. Song, H.-J. Zhang, Chem. Soc. Rev.
2017, 46, 464.
Conflict of Interest [10] K. Liu, X. Zhang, X. Meng, W. Shi, P. Cheng, A. K. Powell, Chem.
Soc. Rev. 2016, 45, 2423.
The authors declare no conflict of interest. [11] Z. Hu, B. J. Deibert, J. Li, Chem. Soc. Rev. 2014, 43, 5815.
[12] Y. J. Cui, Y. F. Yue, G. D. Qian, B. L. Chen, Chem. Rev. 2012, 112, 1126.
[13] Y. Chen, S. Zhang, S. Cao, S. Li, F. Chen, S. Yuan, C. Xu, J. Zhou,
X. Feng, X. Ma, B. Wang, Adv. Mater. 2017, 29, 1606221.
Keywords [14] Y. M. Zhang, S. Yuan, G. Day, X. Wang, X. Y. Yang, H. C. Zhou,
fluorescence, lanthanides, metal-organic frameworks, multicenter Coord. Chem. Rev. 2018, 354, 28.
emissions, ratiometric sensors [15] W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li,
S. K. Ghosh, Chem. Soc. Rev. 2017, 46, 3242.
Received: September 10, 2018 [16] B. Yan, Acc. Chem. Res. 2017, 50, 2789.
Revised: January 15, 2019 [17] E. J. McLaurin, L. R. Bradshaw, D. R. Gamelin, Chem. Mater. 2013,
Published online: February 21, 2019 25, 1283.

Adv. Mater. 2020, 32, 1805871 1805871  (12 of 14) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[18] A. C. Sedgwick, L. Wu, H. Han, S. D. Bull, X. He, T. D. James,
J. L. Sessler, B. Z. Tang, H. Tian, J. Yoon, Chem. Soc. Rev. 2018, 47,
8842.
[19] F. Yi, D. Chen, M. Wu, L. Han, H. Jiang, ChemPlusChem 2016, 81,
675.
[20] Y. J. Cui, H. Xu, Y. F. Yue, Z. Y. Guo, J C. Yu, Z. X. Chen, J. K. Gao,
Y. Yang, G. D. Qian, B. L. Chen, J. Am. Chem. Soc. 2012, 134, 3979.
[21] X. T. Rao, T. Song, J. K. Gao, Y. J. Cui, Y. Yang, C. D. Wu, B. L. Chen,
G. D. Qian, J. Am. Chem. Soc. 2013, 135, 15559.
[22] J.-M. Zhou, W. Shi, N. Xu, P. Cheng, Inorg. Chem. 2013, 52, 8082.
[23] S.-N. Zhao, L.-J. Li, X.-Z. Song, M. Zhu, Z.-M. Hao, X. Meng,
L.-L. Wu, J. Feng, S.-Y. Song, C. Wang, H.-J. Zhang, Adv. Funct.
Mater. 2015, 25, 1463.
[24] J. Zhou, H. Li, H. Zhang, H. Li, W. Shi, P. Cheng, Adv. Mater. 2015,
27, 7072.
[25] S. Y. Zhang, W. Shi, P. Cheng, M. J. Zaworotko, J. Am. Chem. Soc.
2015, 137, 12203.
[26] M. C. Heffern, L. M. Matosziuk, T. J. Meade, Chem. Rev. 2014, 114,
4496.
[27] Y. Zhang, B. Li, H. Ma, L. Zhang, Y. Zheng, Biosens. Bioelectron.
2016, 85, 287.
[28] D. B. Wang, Q. H. Tan, J. J. Liu, Z. L. Liu, Dalton Trans. 2016, 45,
18450.
[29] Z. R. Yang, M. M. Wang, X. S. Wang, X. B. Yin, Anal. Chem. 2017,
89, 1930.
[30] X. Zhang, Q. Hu, T. F. Xia, J. Zhang, Y. Yang, Y. J. Cui, B. L. Chen,
G. D. Qian, ACS Appl. Mater. Interfaces 2016, 8, 32259.
[31] J. N. Hao, B. Yan, Nanoscale 2016, 8, 12047.
[32] X. Y. Xu, B. Yan, J. Mater. Chem. A 2017, 5, 2215.
[33] W. Q. Zhang, Q. Y. Li, J. Y. Cheng, K. Cheng, X. Y. Yang, Y. W. Li,
X. S. Zhao, X. J. Wang, ACS Appl. Mater. Interfaces 2017, 9, 31352.
[34] H. Zhang, C. S. Lin, T. L. Sheng, S. M. Hu, C. Zhuo, R. B. Fu,
Y. H. Wen, H. R. Li, S. D. Su, X. T. Wu, Chem. – Eur. J. 2016, 22,
4460.
[35] Y. Cheng, Y. Gao, H. Lin, F. Huang, Y. Wang, J. Mater. Chem. C
2018, 6, 7462.
[36] X. Cui, Y. Cheng, H. Lin, F. Huang, Q. Wu, Y. Wang, Nanoscale
2017, 9, 13794.
[37] X. Cui, Y. Cheng, H. Lin, F. Huang, Q. Wu, J. Xu, Y. Wang, Sens.
Actuators, B 2018, 256, 498.
[38] Q. L. Zhu, Q. Xu, Chem. Soc. Rev. 2014, 43, 5468.
[39] J. C. Yu, Y. J. Cui, H. Xu, Y. Yang, Z. Y. Wang, B. L. Chen, G. D. Qian,
Nat. Commun. 2013, 4, 2719.
[40] E. Haque, V. Lo, A. I. Minett, A. T. Harris, T. L. Church, J. Mater.
Chem. A 2014, 2, 193.
[41] W. Xie, W. W. He, S. L. Li, K. Z. Shao, Z. M. Su, Y. Q. Lan, Chem. –
Eur. J. 2016, 22, 17298.
[42] D. M. Chen, N. N. Zhang, C. S. Liu, M. Du, ACS Appl. Mater. Inter-
faces 2017, 9, 24671.
[43] M. J. Dong, M. Zhao, S. Ou, C. Zou, C. D. Wu, Angew. Chem., Int.
Ed. 2014, 53, 1575.
[44] M. Bagheri, M. Y. Masoomi, A. Morsali, Sens. Actuators, B 2017,
243, 353.
[45] Y. J. Cui, R. J. Song, J. C. Yu, M. Liu, Z. Q. Wang, C. D. Wu, Y. Yang,
Z. Y. Wang, B. L. Chen, G. D. Qian, Adv. Mater. 2015, 27, 1420.
[46] X. Y. Xu, X. Lian, J. N. Hao, C. Zhang, B. Yan, Adv. Mater. 2017, 29,
1702298.
[47] S. J. Zhu, Q. N. Meng, L. Wang, J. H. Zhang, Y. B. Song, H. Jin,
K. Zhang, H. C. Sun, H. Y. Wang, B. Yang, Angew. Chem., Int. Ed.
2013, 52, 3953.
[48] Y. Fang, S. Guo, D. Li, C. Zhu, W. Ren, S. Dong, E. Wang, ACS Nano
2012, 6, 400.
[49] S. T. Yang, X. Wang, H. F. Wang, F. S. Lu, P. G. Luo, L. Cao,
M. J. Meziani, J. H. Liu, Y. F. Liu, M. Chen, Y. Huang, Y. P. Sun,
J. Phys. Chem. C 2009, 113, 18110.
Adv. Mater. 2020, 32, 1805871 1805871  (13 of 14)
www.advmat.de
[50] Q. Li, T. Y. Ohulchanskyy, R. Liu, K. Koynov, D. Wu, A. Best,
R. Kumar, A. Bonoiu, P. N. Prasad, J. Phys. Chem. C 2010, 114,
12062.
[51] H. Li, X. He, Z. Kang, H. Huang, Y. Liu, J. Liu, S. Lian,
C. H. A. Tsang, X. Yang, S. T. Lee, Angew. Chem., Int. Ed. 2010, 49,
4430.
[52] Y. Dong, R. Wang, G. Li, C. Chen, Y. Chi, G. Chen, Anal. Chem.
2012, 84, 6220.
[53] L. Cao, M. J. Meziani, S. Sahu, Y. P. Sun, Acc. Chem. Res. 2013, 46,
171.
[54] K. J. McHugh, L. Jing, A. M. Behrens, S. Jayawardena, W. Tang,
M. Gao, R. Langer, A. Jaklenec, Adv. Mater. 2018, 30, 1706356.
[55] X. M. Lin, G. M. Gao, L. Y. Zheng, Y. W. Chi, G. N. Chen, Anal.
Chem. 2014, 86, 1223.
[56] L. H. Xu, G. Z. Fang, J. F. Liu, M. F. Pan, R. R. Wang, S. Wang,
J. Mater. Chem. A 2016, 4, 15880.
[57] Y. Q. Dong, J. H. Cai, Q. Q. Fang, X. You, Y. W. Chi, Anal. Chem.
2016, 88, 1748.
[58] X. Y. Xu, B. Yan, J. Mater. Chem. C 2016, 4, 1543.
[59] J. X. Wu, B. Yan, Dalton Trans. 2017, 46, 7098.
[60] W. A. Maza, R. Padilla, A. J. Morris, J. Am. Chem. Soc. 2015, 137,
8161.
[61] R. Chen, J. F. Zhang, J. Chelora, Y. Xiong, S. V. Kershaw, K. F. Li,
P. K. Lo, K. W. Cheah, A. L. Rogach, J. A. Zapien, C. S. Lee, ACS
Appl. Mater. Interfaces 2017, 9, 5699.
[62] H. Q. Yin, J. C. Yang, X. B. Yin, Anal. Chem. 2017, 89, 13434.
[63] H. Zhao, J. Ni, J. J. Zhang, S. Q. Liu, Y. J. Sun, H. J. Zhou, Y. Q. Li,
C. Y. Duan, Chem. Sci. 2018, 9, 2918.
[64] X. Xu, B. Yan, Adv. Funct. Mater. 2017, 27, 1700247.
[65] J. Wang, H. Y. Chen, F. Ru, Z. Zhang, X. Mao, D. L. Shan, J. Chen,
X. Q. Lu, Chem. – Eur. J. 2018, 24, 3499.
[66] H. S. Jung, P. Verwilst, W. Y. Kim, J. S. Kim, Chem. Soc. Rev. 2016,
45, 1242.
[67] A. Douvali, A. C. Tsipis, S. V. Eliseeva, S. Petoud,
G. S. Papaefstathiou, C. D. Malliakas, I. Papadas, G. S. Armatas,
I. Margiolaki, M. G. Kanatzidis, T. Lazarides, M. J. Manos, Angew.
Chem., Int. Ed. 2015, 54, 1651.
[68] S. G. Dunning, A. J. Nuñez, M. D. Moore, A. Steiner, V. M. Lynch,
J. L. Sessler, B. J. Holliday, S. M. Humphrey, Chem 2017, 2, 579.
[69] J. Han, K. Burgess, Chem. Rev. 2010, 110, 2709.
[70] J. R. Casey, S. Grinstein, J. Orlowski, Nat. Rev. Mol. Cell Biol. 2010,
11, 50.
[71] B. A. Webb, M. Chimenti, M. P. Jacobson, D. L. Barber, Nat. Rev.
Cancer 2011, 11, 671.
[72] J. Wang, Y. Li, M. Jiang, Y. H. Liu, L. W. Zhang, P. Y. Wu, Chem. –
Eur. J. 2016, 22, 13023.
[73] T. F. Xia, F. L. Zhu, K. Jiang, Y. J. Cui, Y. Yang, G. D. Qian, Dalton
Trans. 2017, 46, 7549.
[74] Y. Lu, B. Yan, Chem. Commun. 2014, 50, 13323.
[75] Y. Su, J. Yu, Y. Li, S. F. Z. Phua, G. Liu, W. Q. Lim, X. Yang,
R. Ganguly, C. Dang, C. Yang, Y. Zhao, Commun. Chem. 2018,
1, 12.
[76] J. Q. Tian, Q. Liu, A. M. Asiri, A. O. Al-Youbi, X. P. Sun, Anal. Chem.
2013, 85, 5595.
[77] E. Gaggelli, H. Kozlowski, D. Valensin, G. Valensin, Chem. Rev.
2006, 106, 1995.
[78] R. R. Crichton, D. T. Dexter, R. J. Ward, Coord. Chem. Rev. 2008, 252,
1189.
[79] E. M. Nolan, S. J. Lippard, Chem. Rev. 2008, 108, 3443.
[80] I. Onyido, A. R. Norris, E. Buncel, Chem. Rev. 2004, 104,
5911.
[81] C. Bresner, S. Aldridge, I. A. Fallis, C. Jones, L. L. Ooi, Angew.
Chem., Int. Ed. 2005, 44, 3606.
[82] X. Lian, B. Yan, Dalton Trans. 2016, 45, 18668.
[83] L. Mølhave, B. Bach, O. F. Pedersen, Environ. Int. 1986, 12, 167.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
[84] H. Guo, S. C. Lee, L. Y. Chan, W. M. Li, Environ. Res. 2004,
94, 57.
[85] V. J. Cogliano, Y. Grosse, R. A. Bean, K. Straif, M. B. Secretan,
F. E. Ghissassi, Environ. Health Perspect. 2005, 113, 1205.
[86] G. Yang, L. Wu, B. Jiang, W. Yang, J. Qi, K. Cao, Q. Meng,
A. K. Mustafa, W. Mu, S. Zhang, S. H. Snyder, R. Wang, Science
2008, 322, 587.
[87] V. S. Lin, W. Chen, M. Xian, C. J. Chang, Chem. Soc. Rev. 2015, 44, 4596.
[88] X. B. Zheng, R. Q. Fan, Y. Song, A. Wang, K. Xing, X. Du, P. Wang,
Y. L. Yang, J. Mater. Chem. C 2017, 5, 9943.
[89] Z. Hu, B. J. Deibert, J. Li, Chem. Soc. Rev. 2014, 43, 5815.
[90] Y. Li, S. Zhang, D. Song, Angew. Chem., Int. Ed. 2013, 52, 710.
Adv. Mater. 2020, 32, 1805871 1805871  (14 of 14)
www.advmat.de
[91] Y. H. Zhang, B. Li, H. P. Ma, L. M. Zhang, W. X. Zhang, J. Mater.
Chem. C 2017, 5, 4661.
[92] G. B. Mills, W. H. Moolenaar, Nat. Rev. Cancer 2003, 3, 582.
[93] Y. H. Zhang, B. Li, H. P. Ma, L. M. Zhang, H. Jiang, H. Song,
L. G. Zhang, Y. S. Luo, J. Mater. Chem. C 2016, 4, 7294.
[94] M. Jin, Z. L. Mou, R. L. Zhang, S. S. Liang, Z. Q. Zhang, Biosens.
Bioelectron. 2017, 91, 162.
[95] Y. X. Gao, G. Yu, K. Liu, B. Wang, Sens. Actuators, B 2018, 257,
931.
[96] M. Rekharsky, H. Yamamura, M. Kawai, Y. Inoue, J. Am. Chem. Soc.
2001, 123, 5360.
[97] H. Weng, B. Yan, Sens. Actuators, B 2017, 253, 1006.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim