A Highly Sensitive Luminescent Dye@MOF Composite for Probing Different Volatile Organic Compounds

Article abstract of DOI:10.1002/cplu.201600057

The probing of volatile organic compounds (VOCs) is critical and challenging in biotechnology and environmental monitoring. Incorporation of luminescent moieties into metal–organic frameworks (MOFs) has produced many unique luminescent sensors for probing

Full text of DOI:10.1002/cplu.201600057

DOI: 10.1002/cplu.201600057
Full Papers
A Highly Sensitive Luminescent Dye@MOF Composite for
Probing Different Volatile Organic Compounds
Jun-Ping Zheng, Sha Ou, Min Zhao, and Chuan-De Wu*[a]
The probing of volatile organic compounds (VOCs) is critical
and challenging in biotechnology and environmental monitor-
ing. Incorporation of luminescent moieties into metal–organic
frameworks (MOFs) has produced many unique luminescent
sensors for probing different VOCs. The emissions of most
MOF sensors are based mainly on the single transitions of lu-
minescent moieties, so the luminescence readouts are only
predominant for some special VOCs. We use a natural amino
acid derivative as the luminescent moiety to result in a lamellar
coordination polymer, and further embed luminescent dye
molecules in the crystal matrix to result in a luminescent
dye@MOF sensor. The composite sensor exhibits excellent sen-
sitivity for decoding different VOCs with clearly differentiable
fluorescence emission by tuning the energy transfer efficiency
from the organic ligand to the dye moieties. The composite lu-
minescent sensor is self-calibrated, and much more stable and
instantaneous than other more widely explored luminescent
sensors.
Introduction
Most volatile organic compounds (VOCs) are poisonous and
harmful substances. The development of highly sensitive and
fast-response probing sensors for the detection of VOCs is
highly desirable for reducing the discharge of VOCs and moni-
toring the content of VOCs, and the choice of sensor materials
is central to achieving highly efficient probing of VOCs.[1]
Recent work has proved that fluorescence probing based on
the sensor–VOC interactions is a powerful detection method.[2]
The challenge is how to improve the sensitivity of fluorescence
sensors for probing different VOCs, especially for those VOCs
with similar chemical and physical properties, such as homo-
logue and isomeride VOCs.
the luminescent moieties. Our strategy is to introduce second
luminescent moieties in MOFs as reference emission centers,
to improve the luminescent sensitivity of MOF sensors.[11] If the
emission bands of the organic ligands match the excitation
bands of the second luminescent moieties in MOFs, the sensi-
tivity of MOF sensors can be improved significantly in terms of
the probing of different VOCs by tuning the energy transfer ef-
ficiency from the first to the second luminescent moieties.
Herein, we report the synthesis, characterizations, and applica-
tions of a highly sensitive luminescent dye@MOF composite
for probing different VOCs with fast response and excellent se-
lectivity.
Metal–organic frameworks (MOFs) are a class of functional
materials that are self-assembled from organic linkers connect-
ing with metal ions/clusters.[3] By rational design and function-
alization of the constituent moieties, applications of MOFs
have been realized in many fields.[4–8] Taking the solvent-de-
pendent optical properties of luminescent moieties, MOFs
have been used as probing sensors for the detection of many
VOCs.[9,10] MOF sensors have the distinct advantages of fast re-
sponse, high sensitivity, and noninvasive operation. The short-
coming is the excitation and emission energy transfers in
MOFs, which are processed mainly in the single-constituent
moieties, resulting in luminescence readouts that are only pre-
dominant to some special VOCs through close contact with
Results and Discussion
Attracted by the special biological activity and the selective
substrate-binding ability of the natural amino acids, we have
used them as building synthons for the construction of homo-
chiral MOFs.[12] To tune the luminescent property and improve
the bridging ability, we have modified the amino acid l-phe-
nylalanine with 2-hydroxybenzaldehyde to result in a chiral
ligand (S)-2-(2-hydroxybenzylamino)-3-phenylpropanoic acid
(H2L) (Scheme 1). The reaction between Zn2+ and H2L resulted
in a layered homochiral MOF [Zn2L2]·H2O (1), which is insoluble
in water and in common organic solvents such as MeOH,
[a] J.-P. Zheng, S. Ou, M. Zhao, Prof. Dr. C.-D. Wu
Center for Chemistry of High-Performance and Novel Materials
Department of Chemistry
Zhejiang University, Hangzhou 310027 (P. R. China)
E-mail: cdwu@zju.edu.cn
Supporting information for this article can be found under http://
dx.doi.org/10.1002/cplu.201600057.
This article is part of a Special Issue on “Coordination Polymers/MOFs“. A
link to the issue will appear here once it is compiled.
Scheme 1. (S)-2-(2-hydroxybenzylamino)-3-phenylpropanoic acid (H2L).
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EtOH, THF, DMF, and so on. The formula was established on
the basis of single-crystal X-ray diffraction, thermogravimetric
analysis (TGA), and elemental analysis. The bulk purity of the
as-synthesized sample was confirmed by powder X-ray diffrac-
tion (PXRD).
Single-crystal X-ray diffraction analysis revealed that com-
pound 1 crystallizes in the nonsymmetric triclinic space group
P1. The asymmetric unit of 1 contains two ZnII cations, two L li-
gands, and one lattice water molecule. The carboxylate group
of L forms a bidentate bridge with two ZnII cations, and the
deprotonated phenol group m2-bridges two Zn centers. As
shown in Figure 1a, the Zn cation is coordinated with two car-
boxyl oxygen atoms from two L ligands, two phenol oxygen
atoms, and one amino group. The five-coordinated ZnII cations
are coupled by two phenol oxygen atoms to form a binuclear
unit {Zn2}. This {Zn2} is further connected with four neighboring
{Zn2} units by carboxylate groups to extend into a 2D lamellar
network propagated in the ab plane (Figure 1b). The lattice
water molecules are imbedded in the void space. There is no
significant interaction between the layered networks except
for the van der Waals contacts (Figure 1c).
The lamellae in compound 1 are connected by van der
Waals interactions, so this provides an opportunity for us to
tune the luminescent property by encapsulating luminescent
dye moieties in the crystal matrix. Molecules of Rhodamine B
dye can be imbedded easily in the as-synthesized sample
(named Rho@1) if Rhodamine B is added into the reaction mix-
ture during the synthesis of 1, as observed by the naked eye
(Figure 2). Analysis by UV/Vis absorption spectroscopy shows
that there is 0.047 wt% imbedded Rhodamine B in Rho@1. The
PXRD pattern of Rho@1 suggests that the main network struc-
ture is basically same as that of 1. Because compound 1 is non-
porous, as suggested by the single-crystal structure and N2
sorption experiments, the loaded dye molecules should be in-
cluded in the MOF crystal matrix. The slight shifts in the diffrac-
tion peak positions suggest that the networks are flexible and
tunable depending on the imbedded substance molecules. No-
tably, Rho@1 is very stable, and the included Rhodamine B
molecules did not leak out upon immersion of Rho@1 in differ-
ent solvents such as EtOH, CH3CN, DMF, and water, as moni-
tored by UV/Vis absorption spectroscopy. If Rhodamine B is im-
bedded in the crystal matrix of Rho@1, the second lumines-
cent transition from the dye can be generated readily, in addi-
tion to the original one in 1. The above properties of Rho@1
are beneficial for its application in the sensing of different
VOCs.
Figure 1. Crystal structure of compound 1: a) views of the coordination
mode of the L ligand and the coordination environment of ZnII ion; b) lamel-
lar network of L linking up Zn binuclear units as viewed down the c axis;
and c) packing diagram as viewed down the a axis. Color codes: Zn, green;
O, red; N, blue; C, deep gray; H, light gray.
The excitation and emission spectra of H2L, 1, and Rho@1
were examined in the solid state at room temperature
(Figure 3). The free H2L ligand displays an intense and broad
band with a maximum at 403 nm in the emission spectrum
under 310 nm UV light excitation, which is attributed to the
electron transition of the H2L ligand involving a ligand-cen-
tered excited state. The light emission peak of 1 shifts to
411 nm upon excitation at 310 nm. The slight redshift of the
emission of L in 1 is attributed to the deprotonation and coor-
dination of L to Zn2+ ions.[13] As expected, the dye-encapsulat-
ed sample Rho@1 simultaneously shows both the characteris-
tic emissions of the dye and L moieties upon excitation at
310 nm in the solid state at room temperature. The emission
bands for the Rhodamine B and L moieties in Rho@1 are
around 583 and 416 nm, respectively. To make comparisons,
we have measured the emission spectra of Rhodamine B and
a thoroughly ground mixture of Rhodamine B and 1 under the
same conditions. Rhodamine B does not display any emission,
whereas the mechanical mixture mainly presents the emission
band of 1 excited at 310 nm in the solid state. These results
demonstrate that the dye molecules were encapsulated in the
crystal matrix of 1. Moreover, isolation of the dye molecules by
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with the excitation energy of the dye in Rho@1, which results
in efficient ligand-to-dye energy transfer.
The emission energy of the dye is mainly transferred from
the L moiety through ligand-to-dye energy transfer, so the
transmission process might be very sensitive to different VOCs
by tuning the energy transfer efficiency between the excited
states of L and Rhodamine B. We used the ground samples of
Rho@1 to study the luminescent sensitivity for probing differ-
ent VOCs. Upon immersion of the samples of Rho@1 in differ-
ent solvents (MeOH, EtOH, phenol, benzyl alcohol, 1,2-dichloro-
benzene, acetonitrile, acetone, THF, and DMF, as shown in
Figure 4), these solid samples emit solvent-dependent fluores-
cence. The emissions of the dye and/or L moieties are clearly
enhanced and/or quenched by different VOCs. In other words,
the emission bands of the L and dye moieties are both varia-
Figure 2. Photo pictures of the crystals of a) compound 1 and b) Rho@1.
Figure 3. Emission spectra of H2L (pink), 1 (black), Rho@1 (blue), dye (green),
and a thoroughly ground mixture of dye and 1 (red), excited at 310 nm in
the solid state at room temperature.
the lamellar networks in Rho@1 can restrain the nonradiative
energy transfer process to prevent fluorescence quenching.[14]
Notably, the emission of the dye is mainly sensitized by the
L moiety in Rho@1. Such a ligand-to-dye energy transfer be-
havior can be modulated systematically by tuning the excita-
tion energy. Upon increasing the excitation wavelength, the
emission intensities of L and the dye changed gradually in the
luminescence spectra of Rho@1. The above results demon-
strate that the emission energy of ligand L ligand matches well
Figure 4. a) Photoluminescence spectra of Rho@1 in the presence of differ-
ent VOCs excited at 310 nm in the solid state at room temperature. b) Emis-
sion peak heights of L (left column) and dye (right column) moieties, and
c) emission peak height ratios of L to dye moieties in the photolumines-
cence spectra of Rho@1 after addition of different VOCs excited at 310 nm
in the solid state at room temperature.
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bles that are dependent on the environmental VOCs, that is,
Rho@1 emits solvent-dependent light colors by tuning the
energy transfer from the ligand to the dye moieties in Rho@1.
Moreover, the distinguishabilities of the luminescence readouts
can be improved by monitoring the relative emission peak
heights of the L to the dye moieties in the luminescence spec-
tra of Rho@1 (Figure 4c). These results demonstrate that intro-
duction of the luminescence reference of dye moieties in
MOFs can increase the probing sensitivity in the detection of
different VOCs by self-referencing the emission peak heights of
different luminescent moieties in the photoluminescence spec-
tra. The composite material Rho@1 is nonporous, so these sol-
vents should mainly be in contact with the solid surface.
We also used Rho@1 to probe different organic sulfides such
as thiol and thioether molecules. As shown in Figure 5, these
smelly and poisonous substances can be differentiated easily
by monitoring the relative emission height ratios of the L to
the dye moieties. Upon mixing the samples of Rho@1 with dif-
ferent amines, as shown in Figure 6, the dye emission is also
fully quenched by the different amine substances. In other
words, the energy transfer from the ligand to dye moieties in
Rho@1 might be cut off by these amines. It is interesting that
these amine molecules have different effects on the emission
of the L moieties, which can be differentiated easily by moni-
toring the emission intensities. Even though different nitroaro-
matic molecules exhibit significant quenching effects on the
emissions of both L and dye in Rho@1, they can also be differ-
entiated easily by monitoring the emission intensities in the lu-
minescence spectra owing to their different quenching effects
(Figure 7). The high sensitivity of Rho@1 is further proved by
probing nitrobenzene in ethanol. Even though the concentra-
tion of nitrobenzene is lowered to 0.01 wt%, the emission
quenching effect is still clear (Figure 8). Moreover, the lumines-
cence emission can also be almost fully quenched upon expo-
sure of Rho@1 to nitrobenzene vapor. The Rho@1 composite
luminescent sensor is very stable, and the luminescence emis-
sion can be regenerated by heating at 608C for 10 min. The re-
covered solid sample can be reused for ten cycles with re-
tained high sensitivity in the probing of nitrobenzene.
Conclusion
In summary, we have synthesized a luminescent lamellar coor-
dination polymer, and further developed a dye@MOF compo-
site luminescent sensor to realize the detection of different
VOCs by monitoring the emissions of different moieties in the
luminescence spectra. The luminescent dye@MOF composite
exhibits excellent sensitivity and distinguishability in probing
different VOCs. The relative emission intensity of L versus the
dye moieties is variable for different solvent molecules in the
luminescence spectra of Rho@1. It is interesting that the inter-
nal reference strategy has overcome the drawback of tradition-
al MOF sensors based on single emission transitions. There are
numerous MOFs and dyes for the construction of luminescent
dye@MOF sensors, so we believe that the internal reference
strategy is a very promising approach for the development of
highly sensitive composite sensors.
Figure 5. a) Photoluminescence spectra of Rho@1 in the presence of differ-
ent thiol and thioether molecules excited at 310 nm in the solid state at
room temperature. b) Emission peak heights of L (left column) and dye (right
column) moieties, and c) the emission peak height ratios of L to dye moiet-
ies in the photoluminescence spectra of Rho@1 after addition of different
thiol and thioether molecules excited at 310 nm in the solid state at room
temperature.
Experimental Section
Materials and measurements
All the chemicals were obtained from commercial sources and
were used without further purification. Elemental analyses were
performed with a ThermoFinnigan Flash EA 1112 elementary ana-
lyzer. FTIR spectra were recorded from KBr pellets on a FTS-40
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a heating rate of 108CminÀ1. Powder X-ray diffraction (PXRD) data
were recorded on a RIGAKU D/MAX 2550/PC with CuKa radiation
(l=1.5406 ꢁ). Luminescence spectra of the solid samples were re-
corded on a Hitachi F4600 fluorescence spectrometer at room
temperature. UV/Vis spectra were recorded on a UNICO 2802 spec-
1
trophotometer. The H NMR spectrum was recorded on a 400 MHz
spectrometer in methanol solution, and the chemical shifts were
reported relative to internal standard TMS (0 ppm).
Synthesis of (S)-2-(2-hydroxybenzylamino)-3-phenylpropano-
ic acid (H2L)
A mixture of 2-hydroxybenzaldehyde (121 mg, 1.0 mmol), l-phenyl-
alanine (166 mg, 1.0 mmol), and NaOH (79 mg, 2.0 mmol) in
a mixed solvent of water (3 mL) and EtOH (3 mL) was stirred at
room temperature for 2 h. Sodium borohydride (76 mg, 20 mmol)
was added to the resulting yellow solution under stirring. The reac-
tion mixture was stirred for 1 h at room temperature, then the pH
value of the solution was adjusted to 5.0 with 10% aqueous HCl
solution. The resulting white solid was filtered, washed with etha-
nol and diethyl ether, and recrystallized in water. Yield: 85.3%; ele-
mental analysis calcd (%) for C15H15NO3: C 70.83, H 6.32, N 5.16;
Figure 6. Photoluminescence spectra of Rho@1 in the presence of different
amine molecules excited at 310 nm in the solid state at room temperature.
1
found: C 71.02, H 6.35, N 5.19; H NMR (400 MHz, CD3OD) d=7.62–
6.40 (m, 9H), 3.75 (d, J=17.6 Hz, 1H), 3.33 (s, 2H), 3.21 (t, J=
13.8 Hz, 1H), 3.08–2.79 ppm (m, 1H); IR (KBr pellet): n˜ =1654(m),
1596(s), 1460(s), 1390(s), 1357(m), 1334(w), 1272(m), 1256(m),
1190(w), 1131(w), 1111(w), 1083(w), 1031(m), 1003(m), 946(m),
874(m), 826(m), 757(s), 699(s), 669(w), 530(m), 490(w) cmÀ1
.
Synthesis of [Zn2L2]·H2O (1)
H2L (54 mg, 0.2 mmol) and Zn(NO3)2·6H2O (60 mg, 0.2 mmol) were
thoroughly dissolved in a mixed solvent of EtOH (5 mL) and DMF
(3 mL). An aqueous solution of NaOH (0.3 mL, 0.05 molLÀ1) was
added dropwise to the solution under stirring. The resulting mix-
ture was heated at 658C for three days. Colorless crystals of 1 were
isolated by filtration, washed with EtOH, and dried in air. Yield:
76%; elemental analysis calcd (%) for C32H32N2O7Zn2: C 56.13, H
4.71, N 4.09; found: C 55.86, H 4.75, N 4.13; IR (KBr pellet): n˜ =
1655(m), 1598(s), 1582(s), 1486(s), 1451(s), 1414(m), 1382(w),
1276(s), 1095(w), 1053(w), 875(m), 752(s), 700(s), 595(m),
Figure 7. Photoluminescence spectra of Rho@1 in the presence of different
nitroaromatic molecules excited at 310 nm in the solid state at room tem-
perature.
551(m) cmÀ1
.
X-ray crystal data collection and structure determination
The unit cell determination and data collection for the crystal of
compound 1 were performed on an Oxford Xcalibur Gemini Ultra
diffractometer with an Atlas detector. The data were collected
using graphite-monochromatic enhanced ultra Cu radiation (l=
1.54178 ꢁ) at 293 K. The data sets were corrected by empirical ab-
sorption correction using spherical harmonics, implemented in the
SCALE3 ABSPACK scaling algorithm.[15] The structure of com-
pound 1 was solved by direct methods and refined by full-matrix
least-squares methods with the SHELX-97 program package.[16] All
nonhydrogen atoms were located successfully from Fourier maps.
H atoms were generated geometrically. Crystal data for com-
pound 1: C32H32N2O7Zn2, Mw =687.34, triclinic, space group P1, a=
7.3268(6) ꢁ, b=7.3295(6) ꢁ, c=14.0539(11) ꢁ, a=102.897(7)8, b=
Figure 8. Photoluminescence spectra of Rho@1 in the presence of nitroben-
zene in ethanol with different concentrations and nitrobenzene vapor, excit-
ed at 310 nm in the solid state at room temperature.
91.286(6)8, g=92.116(7)8, V=734.8(1) ꢁ3, Z=1, T=293 K, 1calcd
1.553 gcmÀ3 m=2.443 mmÀ1
F(000)=354, 4634 reflections,
3229 independent reflections, int =0.0288, R1[I>2s(I)]=0.0396,
wR2 =0.0962, GOF=1.199, Flack
parameter=À0.02(4).
=
spectrophotometer in the 4000–400 cmÀ1 region. Thermogravimet-
ric analyses (TGAs) were performed on an SDTQ600 compositional
analysis instrument from 30 to 8008C under a N2 atmosphere at
,
,
R
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[7] a) Y.-Q. Lan, H.-L. Jiang, S.-L. Li, Q. Xu, Adv. Mater. 2011, 23, 5015; b) Y.
Ikezoe, G. Washino, T. Uemura, S. Kitagawa, H. Matsui, Nat. Mater. 2012,
11, 1081; c) X. Kong, E. Scott, W. Ding, J. A. Mason, J. R. Long, J. A.
Reimer, J. Am. Chem. Soc. 2012, 134, 14341.
CCDC 1451760 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
[8] a) R. Vaidhyanathan, S. S. Iremonger, G. K. H. Shimizu, P. G. Boyd, S. Alavi,
T. K. Woo, Science 2010, 330, 650; b) J. An, S. J. Geib, N. L. Rosi, J. Am.
Chem. Soc. 2010, 132, 38; c) Y.-S. Bae, R. Q. Snurr, Angew. Chem. Int. Ed.
2011, 50, 11586; Angew. Chem. 2011, 123, 11790.
Acknowledgements
We are grateful for the financial support of the National Natural
Science Foundation of China (grant nos. 21373180 and
21525312) and the research fund of the Key Laboratory for Ad-
vanced Technology in Environmental Protection of Jiangsu Prov-
ince (grant no. AE201301).
[9] a) M. D. Allendorf, C. A. Bauer, R. K. Bhakta, R. J. T. Houk, Chem. Soc. Rev.
2009, 38, 1330; b) B. Chen, S. Xiang, G. Qian, Acc. Chem. Res. 2010, 43,
1115; c) Z. Hu, B. J. Deibert, J. Li, Chem. Soc. Rev. 2014, 43, 5815; d) H.-L.
Jiang, Y. Tatsu, Z.-H. Lu, Q. Xu, J. Am. Chem. Soc. 2010, 132, 5586; e) Y.
Li, S. Zhang, D. Song, Angew. Chem. Int. Ed. 2013, 52, 710; Angew. Chem.
2013, 125, 738; f) J. An, C. M. Shade, D. A. Chengelis-Czegan, S. P.
Petoud, N. L. Rosi, J. Am. Chem. Soc. 2011, 133, 1220; g) K. C. Stylianou,
R. Heck, S. Y. Chong, J. Bacsa, J. T. A. Jones, Y. Z. Khimyak, D. Bradshaw,
M. J. Rosseinsky, J. Am. Chem. Soc. 2010, 132, 4119; h) X.-L. Qi, R.-B. Lin,
Q. Chen, J.-B. Lin, J.-P. Zhang, X.-M. Chen, Chem. Sci. 2011, 2, 2214.
[10] a) Y. Cui, Y. Yue, G. Qian, B. Chen, Chem. Rev. 2012, 112, 1126; b) Y. Taka-
shima, V. M. Martꢃnez, S. Furukawa, M. Kondo, S. Shimomura, H. Uehara,
M. Nakahama, K. Sugimoto, S. Kitagawa, Nat. Commun. 2011, 2, 168;
c) Y. Cui, H. Xu, Y. Yue, Z. Guo, J. Yu, Z. Chen, J. Gao, Y. Yang, G. Qian, B.
Chen, J. Am. Chem. Soc. 2012, 134, 3979; d) H. Guo, Y. Zhu, S. Qiu, J. A.
Lercher, H. Zhang, Adv. Mater. 2010, 22, 4190; e) Y.-A. Li, C.-W. Zhao, N.-
X. Zhu, Q.-K. Liu, G.-J. Chen, J.-B. Liu, X.-D. Zhao, J.-P. Ma, S. Zhang, Y.-B.
Dong, Chem. Commun. 2015, 51, 17672.
[11] a) M.-J. Dong, M. Zhao, S. Ou, C. Zou, C.-D. Wu, Angew. Chem. Int. Ed.
2014, 53, 1575; Angew. Chem. 2014, 126, 1601; b) C. Zhan, S. Ou, C.
Zou, M. Zhao, C.-D. Wu, Anal. Chem. 2014, 86, 6648.
[12] a) X.-L. Yang, C.-D. Wu, CrystEngComm 2014, 16, 4907; b) X.-L. Yang, M.-
H. Xie, C. Zou, C.-D. Wu, CrystEngComm 2011, 13, 6422; c) X.-L. Yang,
M.-H. Xie, C. Zou, F.-F. Sun, C.-D. Wu, CrystEngComm 2011, 13, 1570.
[13] J. R. Lakowicz, Principles of Fluorescence Spectoscopy, 3rd ed., Springer,
Berlin, 2006.
Keywords: dyes · luminescence · metal–organic frameworks ·
sensors · volatile organic compounds
[1] a) K. Haupt, K. Mosbach, Chem. Rev. 2000, 100, 2495; b) D. T. McQuade,
A. E. Pullen, T. M. Swager, Chem. Rev. 2000, 100, 2537; c) L. Basabe-Des-
monts, D. N. Reinhoudt, M. Crego-Calama, Chem. Soc. Rev. 2007, 36,
993.
[2] L. You, D. Zha, E. V. Anslyn, Chem. Rev. 2015, 115, 7840.
[3] a) J. R. Long, O. M. Yaghi, Chem. Soc. Rev. 2009, 38, 1213; b) H.-C. Zhou,
J. R. Long, O. M. Yaghi, Chem. Rev. 2012, 112, 673; c) H.-C. Zhou, S. Kita-
gawa, Chem. Soc. Rev. 2014, 43, 5415.
[4] a) G. Fꢂrey, C. Serre, T. Devic, G. Maurin, H. Jobic, P. L. Llewellyn, G. D.
Weireld, A. Vimont, M. Daturi, J.-S. Chang, Chem. Soc. Rev. 2011, 40, 550;
b) T. A. Makal, J.-R. Li, W. Lu, H.-C. Zhou, Chem. Soc. Rev. 2012, 41, 7761.
[5] a) H. Wu, Q. Gong, D. H. Olson, J. Li, Chem. Rev. 2012, 112, 836; b) H.
Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. Knobler,
B. Wang, O. M. Yaghi, Science 2010, 327, 846; c) P. Nugent, Y. Belmabkh-
out, S. D. Burd, A. J. Cairns, R. Luebke, K. Forrest, T. Pham, S. Ma, B.
Space, L. Wojtas, E. Mohamed, M. J. Zaworotko, Nature 2013, 495, 80.
[6] a) L. Ma, C. Abney, W. Lin, Chem. Soc. Rev. 2009, 38, 1248; b) J. Lee, O. K.
Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen, J. T. Hupp, Chem. Soc. Rev.
2009, 38, 1450; c) A. Corma, L. i. Garcia, H. F. X. Xamena, Chem. Rev.
2010, 110, 4606; d) P. Wu, C. He, J. Wang, X. Peng, X. Li, Y. An, C. Duan,
J. Am. Chem. Soc. 2012, 134, 14991; e) G.-Q. Kong, S. Ou, C. Zou, C.-D.
Wu, J. Am. Chem. Soc. 2012, 134, 19851; f) A. Aijaz, A. Karkamkar, Y. J.
Choi, N. Tsumori, E. Rçnnebro, T. Autrey, H. Shioyama, Q. Xu, J. Am.
Chem. Soc. 2012, 134, 13926; g) S. Ou, C.-D. Wu, Inorg. Chem. Front.
2014, 1, 721; h) J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang, C.-Y. Su,
Chem. Soc. Rev. 2014, 43, 6011; i) M. Zhao, S. Ou, C.-D. Wu, Acc. Chem.
Res. 2014, 47, 1199.
[14] N. Chatterton, Y. Bretonniꢄre, J. Pꢂcaut, M. Mazzanti, Angew. Chem. Int.
Ed. 2005, 44, 7595; Angew. Chem. 2005, 117, 7767.
[15] Oxford Diffraction Ltd. CrysAlisPro, Version 1.171.33.56, 2010.
[16] G. M. Sheldrick, Program for Structure Refinement, University of Gçttin-
gen, Gçttingen (Germany), 1997.
Manuscript received: February 4, 2016
Revised: March 7, 2016
Accepted Article published: March 9, 2016
Final Article published: && &&, 0000
&
ChemPlusChem 2016, 81, 1 – 7
www.chempluschem.org
6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
ÝÝ These are not the final page numbers!

FULL PAPERS
Metal–organic framework sensor: We
report an interesting layered coordina-
tion network based on the derivative of
the natural amino acid l-phenylalanine
and zinc ions, which can embed Rhoda-
mine B dye to result in a luminescent
sensor of Rho@MOF composite, which
can detect different volatile organic
compounds with clearly differentiable
and unique luminescence readouts by
tuning the ligand-to-dye energy transfer
(see figure).
J.-P. Zheng, S. Ou, M. Zhao, C.-D. Wu*
&& – &&
A Highly Sensitive Luminescent
Dye@MOF Composite for Probing
Different Volatile Organic Compounds
ChemPlusChem 2016, 81, 1 – 7
www.chempluschem.org
7
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
&
These are not the final page numbers! ÞÞ