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Multifunctional Zinc Metal−Organic Framework Based on Designed

H4TCPP Ligand with Aggregation-Induced Emission Effect: CO2
Adsorption, Luminescence, and Sensing Property
Yangyang Jiang, Libo Sun, Jianfeng Du, Yuchuan Liu, Huaizhong Shi, Zhiqiang Liang,* and Jiyang Li*
State Key Lab of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun, 130012, P. R. China
S Supporting Information
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ABSTRACT: A new rigid and symmetrical tetracarboxylic ligand 2,3,5,6-tetrakis(4-

carboxyphenyl)pyrazine (H4TCPP) with aggregation-induced emission effect has been
designed and synthesized. By using such a ligand, a novel multifunctional metal−organic
framework Zn-TCPP has been successfully constructed. The cross-linkage of dinuclear
Zn2(COO)4 clusters and organic TCPP4− ligands results in the three-dimensional channel
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structure of Zn-TCPP, which has a four connected lvt topology with the point symbol of
{42.84}. Zn-TCPP not only displays bright blue luminescence arising from the matrix
coordination-induced emission effect of the TCPP4− ligand, but also exhibits effective
detection for picric acid and Fe3+ ions. In addition, the activated Zn-TCPP possesses a
highly porous framework with a Brunauer−Emmett−Teller surface area of 984 m2 g−1 and
CO2 adsorption capacity up to 135 cm3 g−1 at 273 K and 732 mmHg. This work
represents a successful example of constructing metal−organic frameworks with desired
functions based on the designed organic ligand.

Metal−organic frameworks (MOFs) are hybrid inorganic−
hydroxyl groups, and N-containing heterocycles) could increase
the affinity between MOFs and CO2.36−39 Furthermore, the
organic crystalline materials composed of metal ions/clusters pore wall could be decorated by functional groups to improve
and organic linkers.1−5 Emerging as a new class of porous the adsorption capacity and selectivity of CO2.40−42
materials, MOFs have attracted more attention in recent years.6 On the other hand, MOFs can be used as sensor materials to
A large variety of MOFs with desired topological frameworks detect and identify the organic species and metal ions. Such
and functions have been synthesized through considering the detection is mainly based on the luminescent quenching or
organic ligand, the framework structure, the surface area, the enhancement of lanthanide ions or the luminescent organic
channel size, and functional groups.7−10 The tunable porous ligands. A notable example is that Li et al. reported the first
structure and the combined advantages of inorganic and highly luminescent MOF to detect nitroaromatic compounds
organic polymers endow MOFs with broad potential 2,4-dinitrotoluene (DNT) and 2,3-dimethyl-2,3-dinitrobutane
applications in gas adsorption/separation,11−14 heterogeneous (DMNB) in the vapor phase.43 Considering the living
catalysis,15 photovoltaic conversion,16−20 molecular magnet- environment and health, the exploitation of bifunctional
ism,21,22 luminescent sensing17,23−26/recognition,27,28 drug/ chemosensors for detecting nitroaromatic compounds that
guest storage,29−32 and so on. can harm personal and environmental safety and the metal ions
Over the past few decades, the rising level of atmospheric (i.e., Fe3+) that are indispensable for the human body are of
CO2 that causes global warming is destroying our living great significance.44
environment.33−35 Thus, decreasing the concentration of CO2 In general, the design and synthesis of functional organic
in the atmosphere is an urgent task, which motivates more ligands is crucial to achieve multifunctional MOFs with CO2
researchers developing various methods and materials for CO2 capture and sensing properties. In the previous reports, the
capture and sequestration. Physical adsorption of CO2 on rigid and highly symmetric tetracarboxylic ligand 4,4′,4″,4‴-
porous solids including molecular sieves, carbon-based benzene-1,2,4,5-tetrayltetrabenzoic acid (H4BTTB) has been
materials, MOFs, and porous organic polymers, has been widely used to synthesize pillared paddlewheel porous MOFs
proven to be an effective and promising approach to alternate with diverse properties such as gas sorption/separation,45
the traditional amine-based chemical absorption that suffers catalysis,46 and energy transfer.47 Tetraphenylethylene-based
high cost, corrosion, and chemical decomposition in the molecules with the aggregation-induced emission (AIE) effect
regeneration process. In various porous materials, MOFs have been utilized to construct luminescent MOFs,48−50 porous
exhibit excellent performance for CO2 adsorption due to
their defined structures, regular channels, and/or cages and Received: January 16, 2017
high surface area. Meanwhile, the presence of unsaturated open Revised: March 6, 2017
metal sites and chemical functionalities (such as acids, amines, Published: March 15, 2017

© 2017 American Chemical Society 2090 DOI: 10.1021/acs.cgd.7b00068

Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design Article

organic polymers (POPs),51−54 and inorganic−organic hybrid geometrically placed with isotropic thermal parameters 1.2 times
materials.55,56 As a new kind of AIEgen, tetraphenylpyrazine that of the attached carbon atom. Attempts to locate and model the
and its derivatives have high symmetry and a rigid skeleton, highly disordered solvent molecules in the pores were unsuccessful.
which can be easily prepared under mild reaction conditions.57 Therefore, the SQUEEZE routine of PLATON was used to remove
the diffraction contribution from guests to produce a set of solvent-free
Therefore, the tetraphenylpyrazine-based carboxylic acid ligand diffraction intensities.61,62 A summary of the crystallographic data and
will show promising prospects in the construction of functional refinement parameters are given in Table S1. The selected bond
MOFs. lengths and angles of Zn-TCPP are given in Table S2. The asymmetric
In this paper, a new tetraphenylpyrazine-based tetracarbox- unit of Zn-TCPP is shown in Figure S1.
ylic ligand 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H4TCPP, Synthesis of 2,3,5,6-Tetrakis(4-(methoxycarbonyl)phenyl)-
Scheme 1) has been designed and synthesized based on the pyrazine. To a solution of vitamin B1 (360 mg, 0.27 mmol) in the
mixture solvent of CH3OH (6 mL) and H2O (2 mL), NaOH (1 mL, 2
M) was dropwise added to adjust the pH to 9−10, and then methyl 4-
Scheme 1. Design and Synthesis Diagram of H4TCPP
formylbenzoate (3.0 g, 18.29 mmol) was added. After being stirred 1 h
Ligand in the ice water bath, the reaction mixture was heated at 60 °C for 1 h
and at 85 °C for 1 h, and the precipitate was formed. After filtering, the
product dimethyl 4,4′-(1-hydroxy-2-oxoethane-1,2-diyl)dibenzoate
was obtained. Then, to a solution of this product (1.64 g, 5.00
mmol) and ammonium acetate (1.155 g, 15.00 mmol) in 5 mL of
acetic acid was added acetic anhydride (765 mg, 7.50 mmol). After
being stirred for 12 h at 120 °C under N2, the precipitate was formed.
Filtration and washing with H2O and diethyl ether afforded 2,3,5,6-
tetrakis(4-(methoxycarbonyl)phenyl)pyrazine as a yellow solid (0.86
g, 1.40 mmol). 1H NMR (300 MHz, CDCl3): δ = 8.01 (dt, J1 = 9.0 Hz,
J2 = 2.1 Hz, 8H), 8.42 (dt, J1 = 8.7 Hz, J2 = 1.8 Hz, 8H), 3.93 (s, 12H).
C NMR (75 MHz, CDCl3): δ = 166.5, 148.2, 141.9, 130.6, 129.9,
129.7, 52.2. C 36 H28 N2 O8 . CHN elemental analysis (%) for
C36H28N2O8: C, 70.12; H, 4.55; N, 4.55. Found: C, 69.74; H, 4.97;
following reasons. First, H4TCPP possesses a rigid skeleton N. 4.46. IR: 3424(w), 3000(w), 2950(m), 2842(w), 1938(w), 1727(s),
1608(m), 1569(w), 1509(w), 1436(m), 1390(m), 1278(s), 1182(m),
similar to H4BTTB and can be easily synthesized from methyl
1116(m), 1016(m), 964(w), 863(m), 829(w), 775(m), 713(m),
4-formylbenzoate.57 Second, there are two N atoms within the 624(w), 538(w), 499(w).
pyrazine core, which is propitious to enhance the adsorption Synthesis of 2,3,5,6-Tetrakis(4-carboxyphenyl)pyrazine. To
ability for CO2 and the sensing selectivity for analytes. Finally a solution of 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)pyrazine
and most importantly, the AIE effect of H4TCPP will endow (1.021 g, 1.66 mmol) in THF-H2O (1:1, 30 mL) was added NaOH
MOFs with interesting luminescent properties. By using this (0.796 g, 19.90 mmol). The mixture was refluxed for about 12 h and
ligand, a new multifunctional Zn-TCPP MOF with lvt topology THF was evaporated. The solution was acidified to pH of 4−5 with
has been successfully constructed. The activated Zn-TCPP HCl (2 M). The precipitate was filtered and washed with H2O to
possesses high CO2 adsorption capacity up to 135 cm3 g−1 at obtain H4TCPP as a yellow solid (0.918 g, 1.64 mmol). 1H NMR (300
273 K and 732 mmHg. Zn-TCPP displays bright blue MHz, DMSO-d6): δ = 13.10 (br, 4H), 7.94 (d, J = 8.4 Hz, 8H), 7.68
(d, J = 8.4 Hz, 8H). 13C NMR (75 MHz, DMSO-d6): δ = 166.9, 148.2,
luminescence benefiting from the matrix coordination-induced 141.5, 131.1, 129.9, 129.3. IR (cm−1): 3453(w), 3002(m), 2657(w),
emission effect of the TCPP4− ligand, which can be used as a 2526(w), 1941(w), 1702(s), 1608(m), 1569(m), 1511(m), 1388(3),
sensor to detect picric acid (PA) and Fe3+ ions.

1317(w), 1176(m), 1010(m), 1106(m), 860(m), 775(m), 717(m),
622(w), 543(m).
EXPERIMENTAL SECTION Synthesis of Zn-TCPP [Zn2(TCPP)(DMF)2]. Zn(NO3)2·6H2O (10
Materials and Characterizations. All the chemicals were of mg, 0.0336 mmol) and H4TCPP (4 mg, 0.0071 mmol) were dissolved
reagent grade quality and obtained from commercial sources without in DMF (1 mL) and ethanol (0.5 mL), and then HNO3 (150 μL, 2.7
further purification. The IR absorption spectra were recorded within M in DMF) was added. The solution was sealed in a 20 mL vial and
the 400−4000 cm−1 region on a Nicolet Impact 410 FTIR heated at 85 °C for 24 h, then cooled to room temperature. Colorless
spectrometer with KBr pellets. Powder X-ray diffraction (PXRD) block-shaped crystals were collected by filtration. The agreement
patterns were collected on a Rigaku D-Max 2550 diffractometer using between the experiment and simulated PXRD patterns indicates the
Cu−Kα radiation (λ = 0.15418 nm) in a 2θ range of 4−40° with a phase purity of as-synthesized Zn-TCPP (Figure S3). IR (cm−1):
scan speed of 12° min−1 at room temperature. The elemental analyses 3448(m), 3066(w), 2931(w), 1660(m), 1616(s), 1531(s), 1405(s),
(C, H, and N) were performed using a PerkinElmer 2400 elemental 1384(s), 1178(w), 1093(m), 1091(m), 1012(m), 865(m), 784(m),
analyzer. Thermogravimetric analyses (TGA) were performed on a 713(m), 595(w), 545(w), 426(w).
TGA Q500 V20.10 Build 36 thermogravimetric analyzer from room Synthesis of the Micrometer-Sized Phase of Zn-TCPP′.
temperature to 800 °C in air atmosphere with a heating rate of 10 °C Zn(NO3)2·6H2O (0.1 g, 0.336 mmol) and H4TCPP (40 mg, 0.071
min−1. Fluorescence measurements were carried out on a SHIMADZU mmol) were dissolved in a mixture of DMF (10 mL) and ethanol (5
RF-5302 PC fluorescence spectrophotometer and FLUOROMAX-4. mL), and then HNO3 (1.5 mL, 2.7 M in DMF) was added. The
The point symbol and topological analysis were conducted using the mixture was sealed in a 100 mL flask and heated at 85 °C with stirring
TOPOS 4.0 program package.58 on an oil bath for 24 h. The powder product was obtained from the
Crystal Structure Determination. Data were collected on a mother liquor by centrifugation and dried in air at room temperature.
BRUKER SMART APEX II CCD diffractometer for Zn-TCPP with PXRD and SEM studies indicated that Zn-TCPP′ has the same
graphite-monochromated Mo Kα radiation (λ = 0.71073 nm). Data structure as that of Zn-TCPP.
processing was accomplished with the SAINT processing program.59 Experiment for the Gas Adsorption Measurements. The N2
The structure was solved by direct method and refined by the full- and CO2 gas adsorption measurements were performed on Micro-
matrix least-squares methods with SHELXTL-97 program package.60 meritics ASAP 2020 surface area and porosity analyzer. Before gas
All non-hydrogen atoms were refined with anisotropic displacement adsorption measurements, the samples were immersed in anhydrous
parameters. The hydrogen atoms on the aromatic rings were ethanol for 7 days to remove the guest molecules in the channels and

2091 DOI: 10.1021/acs.cgd.7b00068

Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design Article

Figure 1. Description of Zn-TCPP structure: (a and b) dinuclear Zn SBU and organic ligand viewed as a pair of 4-c nodes; (c) the 3D framework of
Zn-TCPP; (d) space-filling model of channels along the [001] direction; (e) polyhedral view of the lvt topology; (f) the lvt topology. The
coordinated DMF molecules and H atoms are omitted for clarity (color modes: Zn, green, N, blue, O red, C gray).

then were degassed using the “outgas” function of the surface area characterize the functional groups of Zn-TCPP. As shown in
analyzer at 85 °C for 10 h. Figure S4, the absence of absorption around 1700 cm−1
Experiment for the Luminescent Properties of H4TCPP and demonstrates that the H4TCPP are completely deprotonated.
Zn-TCPP. H4TCPP was well-dispersed in DMF with ultrasound for
about 10 min, and then different amounts of water were added into In addition, the identical IR spectra of Zn-TCPP and Zn-
DMF to detect the AIE effect of H4TCPP. In addition, the same TCPP′ further illustrates that they are isostructural. The SEM
amounts of Zn-TCPP and H4TCPP were pressed into slices to detect image of Zn-TCPP′ displays a rod-like morphology, which
the fluorescence of Zn-TCPP and H4TCPP in the solid state. indicates the crystalline nature as shown in Figure S5. It is
Experiment for the Detection of Nitro Compounds and worth mentioning that Zn-TCPP exhibits high thermal stability
Metal Ions. 0.5 mg of micrometer-size Zn-TCPP′ was well-dispersed
and can be stable up to 350 °C (Figures S6 and S7).
in a solution of 2 mL of ethanol with stirring for about 10 min, and
then diverse amounts of nitroaromatic compounds were added to a Crystal Structure of Zn-TCPP. Single-crystal X-ray
quartz cuvette containing 2 mL of ethanol suspension of Zn-TCPP′ diffraction analysis reveals that Zn-TCPP crystallizes in an
for the luminescent detection experiment. The experiment for the orthorhombic space group of Imma. As shown in Figure 1, its
detection of metal ions is same as that of the detection of nitro framework is composed of paddlewheel dinuclear Zn2(COO)4
compounds. clusters and organic TCPP4− ligands which can be simplified as


Syntheses and Characterizations of H4TCPP, Zn-TCPP,
a pair of 4-c nodes (Figure 1a). Each Zn2(COO)4 cluster is
linked by four organic ligands, and the axial positions of the
cluster are coordinated by two DMF molecules (Figure 1b),
and Zn-TCPP′. As depicted in Scheme 1, 2,3,5,6-tetrakis(4- which could be removed to form unsaturated open metal sites.
(methoxycarbonyl)phenyl)pyrazine was synthesized by the Each organic ligand is linked by four Zn2(COO)4 clusters. The
reaction of methyl 4-formylbenzoate and vitamin B1 under a connection of Zn2(COO)4 clusters and organic ligands
pH of 9−10. Then the ligand of H4TCPP was synthesized by constructs a highly porous framework with interconnected
hydrolysis of 2,3,5,6-tetrakis(4-(methoxycarbonyl)phenyl)- 3D channels along the [001], [010], and [100] directions
pyrazine. The 1H and 13C NMR spectra of H4TCPP prove (Figures 1c,d and S2). It should be noted that these channels
the validation of H4TCPP. The colorless block-shaped Zn- are partially blocked by the coordinated DMF molecules.
TCPP crystals and micrometer-sized phase of Zn-TCPP′ were Calculation by PLATON reveals that the free space per unit
obtained by the solvothermal reaction of H4TCPP and cell is approximately 4669.2 Å3 upon removal of the guest
Zn(NO3)2·6H2O in the presence of HNO3 at 85 °C for 24 molecules, corresponding to 68.0% of the crystal volume
h. The agreement between the experiment and simulated (6864.8 Å3).
PXRD patterns indicates the phase purity of Zn-TCPP and Zn- From the topological perspective, the Zn2(COO)4 cluster
TCPP′ (Figure S3). Infrared spectroscopy is used to can be viewed square geometry, and organic ligand can be
2092 DOI: 10.1021/acs.cgd.7b00068
Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design Article

simplified as a pair of rectangle geometries. The cross-link of new kind of AIEgen would possess the AIE effect. Thus, the
these two geometries results in the 3D (4,4)-connected luminescent behaviors of H4TCPP ligand in DMF−H2O
framework (Figure 1e,f). Meanwhile, topological analysis mixture solvents with different water fractions have been
suggests that Zn-TCPP possesses a four connected lvt topology studied. As shown in Figure 3a, the emission of H4TCPP in
with the point symbol of {42.84}.
Gas Adsorption Property. Inspired by the large void
volume and high thermal stability of Zn-TCPP, the permanent
porosity of activated Zn-TCPP has been explored by using low-
pressure N2 adsorption−desorption at 77 K. Figure 2a and

Figure 3. (a) Luminescent spectra of H4TCPP in DMF−water

mixtures with different water fractions (inset: the luminescent
photograph of H4TCPP in DMF−water mixtures under 365 nm UV
light); (b) luminescent spectra of H4TCPP and Zn-TCPP in the solid

Figure 2. (a) N2 adsorption and desorption isotherms of Zn-TCPP at pure DMF solvent is very weak, but such an emission is
77 K (inset: pore size distribution of activated Zn-TCPP); (b) CO2
enhanced with the addition of water. The strongest emission is
uptakes of Zn-TCPP at 273 and 298 K.
exhibited when the water fraction reaches 35%; afterward, the
emission intensity decreases as the water fraction further
Table S3 shows the N2 sorption isotherm and porous increases. Because water is a poor solvent for H4TCPP, the
properties of the activated Zn-TCPP. According to the addition of water will result in the formation of nanoaggregates
IUPAC classification, it exhibits Type I nitrogen gas sorption of H4TCPP, giving rise to the AIE effect of H4TCPP. The
isotherm with type IV character at higher relative pressure that emission intensity decreases at high water fraction (>40%) may
may be caused in the activation process. The calculated be caused by the presence of four carboxylic acid groups of
Brunauer−Emmett−Teller (BET) surface area is of 984 m2 g−1. H4TCPP.
The pore size distribution of activated Zn-TCPP is calculated In MOF materials, the organic ligands with the AIE effect will
by using nonlocal density functional theory (NLDFT). The show luminescence arising from the matrix coordination-
result indicates that there are three main pores centered at 0.84, induced emission effect.48 As shown in Figure 3b, the solid
1.56, and 1.84 nm, respectively (Figure 2a inset and S2). H4TCPP ligand shows a bright blue emission at 456 nm upon
Furthermore, the CO2 adsorption property of Zn-TCPP has excitation at 386 nm. Meanwhile, Zn-TCPP displays a slight
been investigated. The adsorption amounts of CO2 reach 135 blue-shifted emission at 449 nm compared with H4TCPP with
and 101 cm3 g−1 at 273 and 298 K under 732 mmHg, excitation upon 391 nm. The quantum yield of H4TCPP in the
respectively (Figure 2b), which is comparable to the value of solid state is 3.08%, while this value of Zn-TCPP increases to
Zn-BTTB (128 cm3 g−1 at 273 K and 1 atm).63 The isosteric 6.55%. These results are mainly caused by the restriction of
heat (Qst) of adsorption for Zn-TCPP has been calculated by intramolecular rotation of TCPP4− due to the coordination of
fitting the CO2 adsorption isotherms measured at 273 and 298 carboxyl group with Zn ions. In addition, the framework of Zn-
K to the virial equation (Figure S8). At zero-coverage, the Qst of TCPP keeps the TCPP4− ligands separated well with a certain
CO2 for Zn-TCPP is 19.8 kJ mol−1 (Figure S9). distance, thus decreasing the intermolecular luminescent
AIE Effect of H4TCPP and Luminescent Property of quenching of TCPP4−. This indicates that MOFs constructed
Zn-TCPP. According to the restriction of intramolecular by AIE-based ligands will present excellent luminescence than
rotation (RIR) mechanism of AIE, the H4TCPP ligand as a that of the organic ligand itself.
2093 DOI: 10.1021/acs.cgd.7b00068
Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design Article

Detection for Nitroaromatic Compounds and Metal

Ions. Encouraged by the luminescence of Zn-TCPP, its
selective sensing ability for various nitroaromatic compounds
and metal ions has been studied. Picric acid (PA), 2,4-
dinitrophenol (2,4-DNP), 2,4-dinitrotoluene (2,4-DNT), 4-
nitrotoluene (4-NT), 4-nitrobenzaldehyde (4-NBA), and
nitrobenzene (NB) are selected as detection candidates for
nitroaromatic compounds. Micrometer-size phase of Zn-
TCPP′ can be well dispersed in ethanol to form a
homogeneous suspension. As shown in Figure 4, different

Figure 4. Luminescent quenching intensity (plotted as quench Figure 5. (a) Luminescent quenching of Zn-TCPP′ dispersed in
percentage) of Zn-TCPP′-ethanol suspension in the presence of ethanol by gradual addition of PA−ethanol solution ([PA] = 1 × 10−3
different nitroaromatic compounds with a concentration of 56.60 μM. M); (b) Stern−Volmer plot of Io/I versus PA concentration in Zn-
TCPP′−ethanol suspension (inset: the selected area enlarged view).
degrees of fluorescence quenching of Zn-TCPP′-ethanol
suspension can be observed. And the extent of quenching is In addition, we also studied the sensing ability of Zn-TCPP
in the following order: PA > 2,4-DNP > 2,4-DNT > 4-Cl-NB > for various metal ions by using the same method. The
4-NBA > 4-NT. Among these nitroaromatic compounds, PA luminescent spectra of Zn-TCPP′ immersed in the solutions of
shows the most effective quenching about 77.8%. The reason different nitrate salts of Fe3+, Cd2+, Cr3+, Zn2+, Sr2+, In3+, Ni2+,
may be that there are two free N groups of pyrazine on the pore Co2+, Ba2+, Li+, Mg2+, and FeCl2 with concentrations of 56.60
surface, which favors interaction with the hydroxyl group of PA, μM have been shown in Figure 6. A luminescent quenching of
thus enhancing the charge transfer effect from the excited state
of the electron donating Zn-TCPP framework to electron
withdrawing PA molecules.
To further investigate the sensing ability of Zn-TCPP′ for
PA, the emission spectra are measured by the gradual addition
of PA solution into a suspension of 0.5 mg of Zn-TCPP′
dispersed in 2 mL of an ethanol solution. As shown in Figure
5a, the fluorescent intensity obviously decreases with the
increasing PA amount. When the concentration of PA reaches
5.98 μM, 12.7% quenching could be observed. The Stern−
Volmer plot of relative luminescent intensity (Io/I, Io, and I are
the luminescence intensities of Zn-TCPP′ suspension before
and after the addition of PA, respectively) and the
concentration of PA are shown in Figure 5b. The Stern− Figure 6. Luminescent quenching intensity (plotted as quench
Volmer plot is almost linear at the low concentration and is an percentage) of Zn-TCPP′−ethanol suspension in the presence of
upward curve at the higher concentration, indicating that the different metal ions with a concentration of 56.60 μM.
quenching mechanism can be explained by a combination of
dynamic and static mechanisms. The quenching constant (Ksv, 39% is observed in the presence of Fe3+ ions, which is
Io/I = 1 + Ksv × [M], where [M] is the molar concentration of significantly more than other metal ions. It is noted that the
Zn-TCPP′ for PA) at low concentration is 3.59 × 104 M−1, existence of Fe3+ ion or PA will decrease the crystallinity of Zn-
which is comparable to those of previously reported MOF- TCPP′, but the Zn-TCPP framework is kept intact (Figure
based sensors, such as UIO-67-dcppy (2.9 × 104 M−1),64 S13). The luminescent intensity of Zn-TCPP′ could be
[Cd(NDC)0.5(PCA)] (3.5 × 104 M−1),65 and [Tb(1,3,5-BTC)] regenerated after washing with ethanol, which illustrates the
(3.42 × 104 M−1).66 reusability of Zn-TCPP′ for sensing of Fe3+ in ethanol (Figure
2094 DOI: 10.1021/acs.cgd.7b00068
Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design


S12). For better understanding of the selectively sensing ability ASSOCIATED CONTENT
of Zn-TCPP′ for Fe3+ ions, the luminescent titration of the Zn- *
S Supporting Information
TCPP′ suspension in ethanol has been investigated with the The Supporting Information is available free of charge on the
gradual addition of Fe3+-ethanol solution. As shown in Figure ACS Publications website at DOI: 10.1021/acs.cgd.7b00068.
7a, the luminescent intensity decreases gradually with the
The crystal data and structure refinement, the selected
bond lengths and angles. The asymmetric unit, PXRD
patterns, TGA, and IR spectra of Zn-TCPP. Lumines-
cent titrations of different volume of NAC for Zn-TCPP
in ethanol suspensions (PDF)
Accession Codes
CCDC 1516214 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via, or by emailing data_, or by contacting The Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: +44 1223 336033.

Corresponding Authors
*E-mail: (Z.L.).
*E-mail: (J.L.).
Zhiqiang Liang: 0000-0003-4473-8544
The authors declare no competing financial interest.

We thank the National Natural Science Foundation of China
(Grants: 21471064, 21671075 and 21621001) for support to
this work.

(1) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Figure 7. (a) Luminescent quenching of Zn-TCPP′ dispersed in Eddaoudi, M.; Kim, J. Nature 2003, 423, 705−714.
ethanol by gradual addition of Fe3+-ethanol solution ([Fe3+] = 1 × (2) Kitagawa, S.; Kitaura, R.; Noro, S. Angew. Chem., Int. Ed. 2004,
10−3 M); (b) Stern−Volmer plot of Io/I versus the concentration of 43, 2334−2375.
Fe3+ in Zn-TCPP′−ethanol suspension. (3) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Chem. Rev.
2012, 112, 1001−1033.
(4) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. Science
increasing concentration of Fe3+ ions. The Stern−Volmer plot 2013, 341, 1230444.
of relative luminescent intensity and the concentration of (5) He, Y. B.; Li, B.; O’Keeffe, M.; Chen, B. L. Chem. Soc. Rev. 2014,
Fe(NO3)3 are shown in Figure 7b. The calculated Ksv is 1.08 × 43, 5618−5656.
104 M−1, which is comparable to some known MOF-based (6) Zhou, H.-C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112,
sensors, such as [La(TPT)(DMSO)2]·H2O (1.36 × 104 673−674.
M−1),67 [La(TAIP)(DMF)2](DMF)0.5 (8.86 × 103 M−1),68 (7) Lu, W. G.; Wei, Z. W.; Gu, Z.-Y.; Liu, T.-F.; Park, J.; Park, J.;
and Eu-MOF-LIC-1 (2.87 × 104 M−1).69 Tian, J.; Zhang, M. W.; Zhang, Q.; Gentle, T., III; Bosch, M.; Zhou,

H.-C. Chem. Soc. Rev. 2014, 43, 5561−5593.
CONCLUSION (8) Bai, Y.; Dou, Y. B.; Xie, L.-H.; Rutledge, W.; Li, J.-R.; Zhou, H.-C.
Chem. Soc. Rev. 2016, 45, 2327−2367.
In conclusion, we have successfully synthesized a novel Zn- (9) Lin, Z.-J.; Lü, J.; Hong, M. C.; Cao, R. Chem. Soc. Rev. 2014, 43,
TCPP MOF by using designed rigid and symmetrical H4TCPP 5867−5895.
ligand containing a pyrazine moiety with an AIE effect. Zn- (10) Tian, D.; Chen, Q.; Li, Y.; Zhang, Y.-H.; Chang, Z.; Bu, X.-H.
TCPP possesses a 3D four connected lvt topology structure, Angew. Chem., Int. Ed. 2014, 53, 837−841.
which is constructed by the connection of dinuclear (11) Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.;
Zn2(COO)4 clusters and organic H4TCPP ligands. The large O’Keeffe, M.; Yaghi, O. M. Science 2008, 319, 939−943.
void volume of Zn-TCPP endows its high BET surface area (12) Li, J.-R.; Sculley, J.; Zhou, H.-C. Chem. Rev. 2012, 112, 869−
and CO2 uptake. Zn-TCPP presents a luminescent property (13) Zhang, Z. J.; Zhao, Y. G.; Gong, Q. H.; Li, Z.; Li, J. Chem.
due to the matrix coordination-induced emission effect of the Commun. 2013, 49, 653−661.
TCPP4− ligand. Such a fluorescent response can be used to (14) Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D.-W. Chem. Rev.
selectively detect PA and Fe3+ ion. This work will prompt 2012, 112, 782−835.
further design of multifunctional MOF materials based on the (15) Lee, J. Y.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S.
tetraphenylpyrazine-based functional organic ligands. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450−1459.

2095 DOI: 10.1021/acs.cgd.7b00068

Cryst. Growth Des. 2017, 17, 2090−2096
Crystal Growth & Design Article

(16) Cui, Y. J.; Yue, Y. F.; Qian, G. D.; Chen, B. L. Chem. Rev. 2012, (48) Shustova, N. B.; McCarthy, B. D.; Dincă, M. J. Am. Chem. Soc.
112, 1126−1162. 2011, 133, 20126−20129.
(17) Rocha, J.; Carlos, L. D.; Paz, F. A. A.; Ananias, D. Chem. Soc. (49) Zhang, M.; Feng, G. X.; Song, Z. G.; Zhou, Y.-P.; Chao, H.-Y.;
Rev. 2011, 40, 926−940. Yuan, D. Q.; Tan, T. T. Y.; Guo, Z. G.; Hu, Z. G.; Tang, B. Z.; Liu, B.;
(18) Sava, D. F.; Rohwer, L. E. S.; Rodriguez, M. A.; Nenoff, T. M. J. Zhao, D. J. Am. Chem. Soc. 2014, 136, 7241−7244.
Am. Chem. Soc. 2012, 134, 3983−3986. (50) Hu, Z. C.; Huang, G. X.; Lustig, W. P.; Wang, F. M.; Wang, H.;
(19) Sun, C.-Y.; Wang, X.-L.; Zhang, X.; Qin, C.; Li, P.; Su, Z.-M.; Teat, S. J.; Banerjee, D.; Zhang, D. Q.; Li, J. Chem. Commun. 2015, 51,
Zhu, D.-X.; Shan, G.-G.; Shao, K.-Z.; Wu, H.; Li, J. Nat. Commun. 3045−3048.
2013, 4, 2717. (51) Dalapati, S.; Gu, C.; Jiang, D. L. Small 2016, 12, 6513−6527.
(20) Stavila, V.; Talin, A. A.; Allendorf, M. D. Chem. Soc. Rev. 2014, (52) Sun, L. B.; Zou, Y. C.; Liang, Z. Q.; Yu, J. H.; Xu, R. R. Polym.
43, 5994−6110. Chem. 2014, 5, 471−478.
(21) Kurmoo, M. Chem. Soc. Rev. 2009, 38, 1353−1379. (53) Sun, L. B.; Liang, Z. Q.; Yu, J. H. Polym. Chem. 2015, 6, 917−
(22) Weng, D.-F.; Wang, Z.-M.; Gao, S. Chem. Soc. Rev. 2011, 40, 924.
3157−3181. (54) Sun, L. B.; Liang, Z. Q.; Yu, J. H. Huaxue Xuebao 2015, 73,
(23) Kreno, L. E.; Leong, K.; Farha, O. K.; Allendorf, M.; Van Duyne, 611−616.
R. P.; Hupp, J. T. Chem. Rev. 2012, 112, 1105−1125. (55) Li, D. D.; Yu, J. H. Small 2016, 12, 6478−6494.
(24) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T. (56) Li, D. D.; Miao, C. L.; Wang, X. D.; Yu, X. H.; Yu, J. H.; Xu, R.
Chem. Soc. Rev. 2009, 38, 1330−1352. R. Chem. Commun. 2013, 49, 9549−9551.
(25) Heine, J.; Müller-Buschbaum, K. Chem. Soc. Rev. 2013, 42, (57) Chen, M.; Li, L. Z.; Nie, H.; Tong, J. Q.; Yan, L. L.; Xu, B.; Sun,
9232−9242. J. Z.; Tian, W. J.; Zhao, Z. J.; Qin, A. J.; Tang, B. Z. Chem. Sci. 2015, 6,
(26) Hu, Z. C.; Deibert, B. J.; Li, J. Chem. Soc. Rev. 2014, 43, 5815− 1932−1937.
(58) Blatov, V. A. Struct. Chem. 2012, 23, 955−963.
(59) SAINT, version 6.02a; Bruker AXS Inc.: Madison, WI, USA,
(27) Jiang, H.-L.; Tatsu, Y.; Lu, Z.-H.; Xu, Q. J. Am. Chem. Soc. 2010,
132, 5586−5587.
(60) Sheldrick, G. M. Acta Crystallogr., Sect. A: Found. Crystallogr.
(28) Chen, B. L.; Xiang, S. C.; Qian, G. D. Acc. Chem. Res. 2010, 43,
2008, 64, 112−122.
1115−1124. (61) Spek, A. L. J. Appl. Crystallogr. 2003, 36, 7−13.
(29) Rocca, J. D.; Liu, D. M.; Lin, W. B. Acc. Chem. Res. 2011, 44, (62) Spek, A. L. Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, 65,
957−968. 148−155.
(30) Horcajada, P.; Gref, R.; Baati, T.; Allan, P. K.; Maurin, G.; (63) Farha, O. K.; Mulfort, K. L.; Hupp, J. T. Inorg. Chem. 2008, 47,
Couvreur, P.; Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 10223−10225.
1232−1268. (64) Nagarkar, S. S.; Desai, A. V.; Ghosh, S. K. Chem. Commun. 2014,
(31) McKinlay, A. C.; Morris, R. E.; Horcajada, P.; Férey, G.; Gref, 50, 8915−8918.
R.; Couvreur, P.; Serre, C. Angew. Chem., Int. Ed. 2010, 49, 6260− (65) Nagarkar, S. S.; Joarder, B.; Chaudhari, A. K.; Mukherjee, S.;
6266. Ghosh, S. K. Angew. Chem., Int. Ed. 2013, 52, 2881−2885.
(32) Wang, H.; Xu, J.; Zhang, D.-S.; Chen, Q.; Wen, R.-M.; Chang, (66) Xiao, J.-D.; Qiu, L.-G.; Ke, F.; Yuan, Y.-P.; Xu, G.-S.; Wang, Y.-
Z.; Bu, X.-H. Angew. Chem., Int. Ed. 2015, 54, 5966−5970. M.; Jiang, X. J. Mater. Chem. A 2013, 1, 8745−8752.
(33) Lü, J.; Perez-Krap, C.; Suyetin, M.; Alsmail, N. H.; Yan, Y.; (67) Zhang, C. Q.; Yan, Y.; Pan, Q. H.; Sun, L. B.; He, H. M.; Liu, Y.
Yang, S. H.; Lewis, W.; Bichoutskaia, E.; Tang, C. C.; Blake, A. J.; Cao, L.; Liang, Z. Q.; Li, J. Y. Dalton Trans. 2015, 44, 13340−13346.
R.; Schröder, M. J. Am. Chem. Soc. 2014, 136, 12828−12831. (68) Wang, D.; Sun, L. B.; Hao, C. Q.; Yan, Y.; Liang, Z. Q. RSC Adv.
(34) Phan, D. T.; Maeder, M.; Burns, R. C.; Puxty, G. Environ. Sci. 2016, 6, 57828−57834.
Technol. 2014, 48, 4623−4629. (69) Hao, J.-N.; Yan, B. J. Mater. Chem. C 2014, 2, 6758−6764.
(35) Qian, D.; Lei, C.; Wang, E.-M.; Li, W.-C.; Lu, A.-H.
ChemSusChem 2014, 7, 291−298.
(36) Britt, D.; Furukawa, H.; Wang, B.; Glover, T. G.; Yaghi, O. M.
Proc. Natl. Acad. Sci. U. S. A. 2009, 106, 20637−20640.
(37) Lee, Y.-G.; Moon, H. R.; Cheon, Y. E.; Suh, M. P. Angew. Chem.,
Int. Ed. 2008, 47, 7741−7745.
(38) Liang, Z. Q.; Du, J. J.; Sun, L. B.; Xu, J.; Mu, Y.; Li, Y.; Yu, J. H.;
Xu, R. R. Inorg. Chem. 2013, 52, 10720−10722.
(39) Zhang, S.-M.; Chang, Z.; Hu, T.-L.; Bu, X.-H. Inorg. Chem.
2010, 49, 11581−11586.
(40) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.;
Bloch, E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Chem. Rev. 2012,
112, 724−781.
(41) Cohen, S. M. Chem. Rev. 2012, 112, 970−1000.
(42) Gao, Q.; Xu, J.; Cao, D. P.; Chang, Z.; Bu, X.-H. Angew. Chem.,
Int. Ed. 2016, 55, 15027−15030.
(43) Lan, A. J.; Li, K. H.; Wu, H. H.; Olson, D. H.; Emge, T. J.; Ki,
W.; Hong, M. C.; Li, J. Angew. Chem., Int. Ed. 2009, 48, 2334−2338.
(44) Song, X.-Z.; Song, S.-Y.; Zhao, S.-N.; Hao, Z.-M.; Zhu, M.;
Meng, X.; Wu, L.-L.; Zhang, H.-J. Adv. Funct. Mater. 2014, 24, 4034−
(45) Mulfort, K. L.; Farha, O. K.; Malliakas, C. D.; Kanatzidis, M. G.;
Hupp, J. T. Chem. - Eur. J. 2010, 16, 276−281.
(46) Shultz, A. M.; Farha, O. K.; Adhikari, D.; Sarjeant, A. A.; Hupp,
J. T.; Nguyen, S. T. Inorg. Chem. 2011, 50, 3174−3176.
(47) Jin, S. Y.; Son, H.-J.; Farha, O. K.; Wiederrecht, G. P.; Hupp, J.
T. J. Am. Chem. Soc. 2013, 135, 955−958.

2096 DOI: 10.1021/acs.cgd.7b00068

Cryst. Growth Des. 2017, 17, 2090−2096