Two 3D Metal-Organic Frameworks Based on CoII and ZnII Clusters for Knoevenagel Condensation Reaction and Highly Selective Luminescence Sensing

Article abstract of DOI:10.1021/acs.cgd.8b00867

Two metal-organic frameworks (MOFs) with 3D structures, {[Co₂₄(BDPO)₁₂(H₂O)₁₂]·18DMF·40H₂O}_n (1) and {[NH₂(CH₃)₂]₄[Zn₃(HBDPO)₂

Full text of DOI:10.1021/acs.cgd.8b00867

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Article
Two 3D Metal-Organic Frameworks based on CoII
and ZnII clusters for Knoevenagel Condensation
Reaction and Highly Selective Luminescence Sensing
Hongming He, Qian-Qian Zhu, Fuxing Sun, and Guangshan Zhu
Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.8b00867 • Publication Date (Web): 14 Aug 2018
Downloaded from http://pubs.acs.org on August 14, 2018
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II
Two 3D MetalꢀOrganic Frameworks based on Co
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II
and Zn clusters for Knoevenagel Condensation
Reaction and Highly Selective Luminescence
Sensing
*
,†
†
*,‡
*,§
Hongming He, QianꢀQian Zhu, Fuxing Sun, and Guangshan Zhu,
† Key Laboratory of InorganicꢀOrganic Hybrid Functional Material Chemistry, Ministry of
Education, Tianjin Key Laboratory of Structure and Performance for Functional Molecules,
College of Chemistry, Tianjin Normal University, Tianjin 300387, People’s Republic of China
‡
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry
Jilin University, Changchun 130012, People’s Republic of China
§ Faculty of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of
China
ABSTRACT: Two MOFs with 3D structures, {[Co (BDPO) (H O) ]•18DMF•40H O}
n
24
12
2
12
2
(
namely 1) and {[NH (CH ) ] [Zn (HBDPO) (SO ) ]} (namely 2), both successfully
2
3 2 4
3
2
4 2
n
II
II
synthesized based on Co and Zn inorganic nodes with the same bridging organic ligand
2
−1
(namely H BDPO). 1 possesses relatively high BET surface area (ca. 1014 m g ) with multiple
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pore systems and basic catalytic centers to apply as an efficient heterogeneous catalytic. The
resultant 2 exhibits a 3D structure based on Zn(COO) and Zn (SO ) (COO) as inorganic
4
2
4 2
2
secondary building units. Thanks to its luminescence property, 2 is able to consider as a platform
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of recyclable biꢀresponsive luminescence sensor for explosive and antibiotics via luminescence
4
quenching effect. The high selectivity of TNP can be estimated by the K value about 1.2 × 10
sv
−
1
M . Significantly, 2 can efficiently detect NFT or NFZ, and the corresponding K values are 4.5
sv
4
4
−1
×
10 and 4.9 × 10 M , respectively.
INTRODUCTION
[
1−5]
Metal−organic frameworks (MOFs)
are fascinating crystal materials and capture the public's
attentions in virtue of their designability, porosity and multiformity. They exhibit various
[6−11]
[12−16]
[17, 18]
potential applications in gas sorption and separation,
catalysis,
enzyme carrier,
[
19, 20]
optical material,
and so on. Notably, MOFs can be easily constructed by the organic ligands
and inorganic metals in the assembly, which both play significantly important influence factors
for the properties of MOFs. The functional groups can be introduced in the organic ligands to
synthesize functional materials for targeting applications. In addition, the different metal ions can
remarkably change the structure and property of MOFs, such as luminescence, catalysis and so
on. MOFs have been widely investigated as heterogeneous catalysts in catalysis fields. Some
MOFs based on some organic ligands with nitrogen atoms have been investigated their basic
[
21−24]
catalytic performance to date.
Triazine ring fragments are always imported into the ligands
[25−30]
as central parts to construct such basic MOFs catalytic.
Nevertheless, there is lots of
demand to study and develop such MOFs to catalyze organic reactions. In addition, luminescent
MOFs possess various advantages, including distinct luminescence spectrum, visible color,
simple operation, high selectivity and sensitivity. Therefore, luminescence MOFs become the
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[31−39]
greatest potential sensor materials towards pollutants, such as explosives and heavy metals.
Many luminescence MOFs have been widely applied as luminescence sensors to detect heavy
metal ions, nitroaromatic compounds (NACs), organic vapors and so on. Notably, antibiotics are
very useful and have a variety of benefits in many fields; however they produce a sequence of
concurrency problems. The residual antibiotics can be founded in agricultural products, food and
river, prompting concerns about the transmission of antibiotic resistance through the food chain
1
1
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[
40, 41]
in human society.
Whereas, only few investigations have been reported to detect antibiotics
[42−49]
by using luminescence MOFs.
Hence, it spurred further sustained attentions to explore
novel sensing MOF materials for efficient detecting antibiotics.
Herein, we firstly prepared two MOFs
Co (BDPO) (H O) ]•18DMF•40H O} (1) and {[NH (CH ) ] [Zn (HBDPO) (SO ) ]} (2)
with
3D
structures,
{
24
12
2
12
2
n
2
3 2 4
3
2
4 2
n
II
II
(
H BDPO = 2,4−bis(3,5−dicarboxyphenylamino)−6−ol triazine) based on Zn and Co metal
4
nodes. The cobalt ion comes from Co(NO ) •6H O, thus the valence of cobalt ion should be +2.
3
2
2
In addition, the whole neutral structure contains Co (BDPO) and the value of BDPO is −4,
24
12
which also confirms that the valence of cobalt ion is +2 in MOF 1.
II
II
As we discussed in the above, due to the different metal ions of Co and Zn , the resultant
samples displayed completely different structures and properties. 1 displayed excellent basic
catalysis ability because of its high surface area with multiple pores and various Lewis basic sites.
On the other hand, the resultant 2 was constructed by the organic ligand and two different
II
Zn(COO)4 and Zn (SO ) (COO) inorganic clusters. Compared with Co ꢀMOFs, the
2
4 2
2
II
luminescence properties of the organic ligand can be well preserved in Zn ꢀMOFs. Hence, 2
exhibited the similar luminescence properties like the free organic ligand H BDPO so that it is
4
considered as a luminescence sensing for explosive and antibiotics.
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Experimental Section
Materials and Methods. All chemicals without any treatment were directly acquired from
companies. The selected organic ligand H BDPO was prepared as the previous reported
4
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28]
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literature. The data of elemental analysis for carbon, hydrogen and nitrogen was collected on a
CEꢀ440 (Leemanꢀlabs) analyzer. Thermogravimetric analysis (TGA) trials were executed on a
−
1
DTG−60A (Shimadzu) instrument in air from 30 to 800 °C (10 °C min ). Fourier−transform
FT) infrared spectra, using KBr as pellets, was performed on an Avatar−370 (Nicolet)
spectrometer. Powder X−ray diffraction (PXRD) patterns were measured on a Rigaku D/maxꢀ
500 diffractometer. Shimadzu UV−2700 spectrophotometer was used to gain UV−Vis results.
(
2
Cary Eclipse fluorescence spectrophotometer was applied for luminescence measurements. The
N , CO and CH sorption measurements were measured on a Micrometrics ASAP 2020 machine.
2
2
4
Gas chromatograph for the catalysis results were collected from Agilent 7890A.
Synthesis of {Co (BDPO) (H O) ]•18DMF•40H O} , 1. Co(NO ) •6H O (0.035 g) and
2
4
12
2
12
2
n
3 2
2
H BDPO (0.02g) were both directly dissolved in DMF/H O (5/0.5 mL) mixed solution in a 20
4
2
mL Teflon−lined autoclave. Another 0.5 mL HNO was further added in the solution. The
3
autoclave was sealed well and heated at 135 °C. The purple block crystals were directly collected
after 4 days (63% yield based on H BDPO). Element analysis of C, N and H for 1
4
(
C H O N Co ). Calc. (%) C, 37.28; N, 12.03; H, 3.72; Found: C, 37.33; N, 12.15; H,
282 338 178 78 24
−
1
3
.79. IR (cm ): 3341 (br), 2931 (s), 1644 (s), 1593 (s), 1557 (s), 1531 (s), 1434 (s), 1375 (s),
1149 (s), 1086 (s), 894 (s), 807 (s), 774 (s), 735 (s), 665 (s), 640 (s), 592 (s), 490 (s) (Figure S1).
Synthesis of {[NH (CH ) ] [Zn (HBDPO) (SO ) ]} , 2. ZnSO •7H O (0.03 g) and H BDPO
2
3 2 4
3
2
4 2
n
4
2
4
(0.02 g) were dissolved in a mixture solution of DMF (5 mL) and EtOH (0.5 mL). The solution
ꢀ1
was added HNO solution (0.6 mL, 2.0 mol L ). Then it was sealed into a 20 mL Teflon
−
lined
3
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autoclave for 3 days at 120°C in an oven to generate colorless pale crystals. The resultant
sample can be collected by simply filtering and washed by fresh DMF several times. The crystal
yield is about 59 % on account of the ligand. Element analysis of C, N and H for 2
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(
C H O N S Zn ): Calc. (%) C, 37.42; N, 13.29; H, 3.53; Found: C, 37.59; N, 13.33; H, 3.52.
46 2 3
52 26 14
−1
IR (cm ): 3134 (br), 2803 (s), 2482 (s), 1708 (s), 1647 (s), 1578 (s), 1560 (s), 1552 (s), 1467 (s),
1
6
364 (s), 1273 (s), 1261 (s), 1234 (s), 1036 (s), 977 (s), 851 (s), 780 (s), 764 (s), 733 (s), 715 (s),
77 (s), 607 (s), 460 (s) (Figure S2).
Typical procedure for catalysis experiments. 1 was soaked into toluene, as reactive solvent,
for one day before using it as a catalytic. Then it was filtered and directly dried in air. Substrate
(0.001 mol) and malononitrile (0.0011 mol) were both added into a glass reactor with 5 mL
toluene. When the reaction temperature reached 80 °C, 1 (0.1 g) was introduced into the reaction
system and stirred at this reaction condition. The GC instrument was employed to analyze the
yields.
Recyclable catalysis experiments. The recyclability of 1 was easily recollected by
centrifugation and washed by fresh toluene after the catalysis experiment. The recollected
samples were reused as a base catalyst.
Luminescence sensing experiments. The powder sample of 2 was dispersed in 3 mL DMF
−1
−1
containing different nitroꢀcompounds (0.01 mol L ) or antibiotics (0.00005 mol L ). The
luminescence results were directly collected after 2 min.
Typical procedure for luminescence titration study. The powder sample of 2 was dispersed in
−1
DMF solution (3 mL, 0.1 mg mL ) and putted into a quartz cell. The quenching experiments
−
1
were performed by gradually adding analyte of NACs (0.001 mol L ), nitrofurantoin (NFT) and
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nitrofurazone (NFZ) (0.001 mol L ) DMF solution. The experiment was parallelly duplicated
three times.
Recyclable luminescence experiments. The recyclability of 2 was explored in DMF solution.
After the first quenching trial, the 2 powder was recollected by centrifugation and washed by
fresh DMF. The recovered crystals were collected and reused in the next quenching experiments.
Single Crystal X-ray Analysis. The structures of 1 and 2 were both measured on Bruker
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SMART APEX II with Cu−K graphite radiation (λ= 1.54184 Å). Adsorption correction was
α
[50]
performed by multi−scan absorption corrections by using SADABS program.
These two
frameworks were determined by direct methods, which was further refined by using the
[
51]
SHELXTL program. The anisotropical technology was used for all non−hydrogen atoms. The
PLATON/SQUEEZE method was applied to delete the contributions from solvent molecules and
[
52, 53]
counter cations.
The solvent−free structure of 1 and 2 were obtained by the SQUEEZE
routine. Crystal data of complex 1 and 2 were both listed in Table 1 and the characteristic bond
lengths and angles are summarized in Table S1.
Table 1 Crystal parameters for 1 and 2.
Compound
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (º)
1
C
9078
Cubic
2
C
282
H
338
O
178
N78Co24
46 52 26 14 2 3
H O N S Zn
1475
Monoclinic
C2/c
30.5668(7)
11.8581(3)
21.7723(5)
90.00
Im−3m
27.9163(6)
27.9163(6)
27.9163(6)
90
β (º)
γ (º)
V (Å )
Z
ρ calc g cm
ꢁ (mm )
Nref
90
90
109.8560(10)
90.00
7422.5(3)
4
1.155
2.256
3
21755.8(9)
24
1.101
7.548
2060
ꢀ
3
ꢀ
1
7330
F(000)
R(int)
Goof
7224.0
0.0866
1.012
2584.0
0.0365
1.047
R
R
1
, wR
, wR
2
[I > 2σ(I)]
(all data)
0.0534, 0.1201
0.0546, 0.1207
0.0742, 0.2071
0.0785, 0.2122
1
2
RESULTS AND DISCUSSION
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Structure {Co (BDPO) (H O) ]•18DMF•40H O} (1). 1 belongs to the cubic Im−3m space
2
4
12
2
12
2
n
group, which contains 1/4 Co1, 1/4 Co2, 1/4 coordinated oxygen atom and 1/4 fully
4
−
deprotonated BDPO organic ligand in the asymmetrical unit (Figure S3). As illustrated in
Figure 1, it contains a very standard and common paddle wheel motif to assemble with the
carboxylic acid groups in the ligand. Interesting, one nitrogen atom form the organic ligand is
further coordinated with one Co site in the paddle wheel motif. It can be found after analysis in
detail that there are three different microporous cages in 1 with 14.9 Å for largest cage, 12.1 Å
for the medium cage, and 8.9 Å for the small one, respectively. All the cages further were
connected by the carboxylate acids and nitrogen atoms in the organic ligands to form a 3D
structure. From the angle of topology, the obtained network is a 5−nodes topology with the point
1
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symbol [4 •6 ]. The total accessible volume of 1 is ca. 49.5% without the guest and coordinated
[
52, 53]
solvents in the PLATON/VOID method.
Due to its distorted solvents and the weak Xꢀray
diffraction data, all solvents can’t be located accurately by the results of the single crystal. Thus,
they only can be inferred by TGA and elemental analysis.
Figure 1. View the large−size cages (a); middle−size cages (b); small−size cages (c), their 3D packing (d) and the whole structure (e) in 1
(hydrogen atoms are deleted for clarity. O, red; Co, blue; C, gray; N, green).
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Structure {[NH (CH ) ] [Zn (HBDPO) (SO ) ]} (2). MOF 2 crystallizes in monoclinic space
2
3 2 4
3
2
4 2
n
2−
group C2/c. The asymmetrical unit of 2 has a half Zn1 cation, one Zn2 cation, one SO4 ion and
3
−
one HBDPO ligand (Figure S4). As shown in Figure 2a, there are two different Zn(COO) and
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Zn (SO ) (COO) clusters as secondary building units. The Zn1 adopt distorted octahedron
2
4 2
2
configuration by six−coordinated oxygen donors from two monodentate and two chelating
carboxylate groups. The Zn2 adopts distorted tetrahedral configuration by four−connected from
2
−
four oxygen atoms from two different SO4 ions and one chelating carboxylate group (Zn−O,
1
.9554−2.8075 Å). In addition, two different Zn2 ions were further connected by two shared
2−
2−
SO4 ions to form a binuclear inorganic cluster (Zn−O, 1.9502−2.6768 Å). Hence, the SO4 ion
II
plays a necessary role for the coordinated process between Zn ions and ligands. The Zn⋅⋅⋅Zn
3−
distance in the binuclear inorganic cluster is 4.5098 Å. The partial deprotonated HBDPO only
1
1
1
1
1
adopts one coordinated mode (ꢀ3−η : η : η : η : η , Figure 2b) to connect with three different
Zn(II) ions. Meanwhile, the ligands can link with these two Znꢀclusters to form an interesting 3D
construction (Figure 2c). However, the solvents in 2 are also hard to directly make sure, which
are further able to determine from the results of elemental analysis, FT−IR and TGA data.
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9
0
3−
Figure 2. (a) Two different Zn(COO)
4
and Zn
2 4 2 2
(SO ) (COO) clusters; (b) the coordinated mode of partial deprotonated HBDPO ; (c) the 3D
structure of 2 (N: blue; Zn: green; O: red; C: gray; S: yellow).
Thermal and chemical stability.
MOF 1 loses about 24.68% weight before 240 °C, which is similar with the calculated result
after removing coordinated and guest molecules (calculated 24.79%, Figure S5). As illustrated in
Figure S6, the TGA data of 2 shows a 12.49% weight lose before 250 °C, which is similar with
the calculated result after removing guest cations and molecules (calculated 12.74%). The phase
purity of the experimental sample can be determined by PXRD patterns based on their
characteristic diffraction peaks (Figures S7 and S8). The PXRD results demonstrated the purity
of MOFs 1 and 2.
Gas sorption properties.
1
and 2 were both directly exchanged the high boiling point guest molecules with the low boiling
point CH Cl for two days. These MOFs were heated at 100 °C under vacuum for 12 h. The N
2
2
2
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6
gas sorption measurement of the activated 1 was implemented to verify the permanent pore
character at 77 K. N sorption isotherms at 77 K featured a completely reversible type−I
2
adsorption characteristic of microporous materials (Figure 3). The BET and Langmuir surface
2
−1
0
1
2
3
4
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0
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9
0
area are calculated directly as 1014 and 1147 m g , respectively. The corresponding pore width
distributions are 7.3, 11.8 and 14.8 Å through the DFT method. The structure of the activated
sample can be retained well by the PXRD measurement (Figure S9). It also exhibits more
excellent CO adsorption capacity than the adsorption amount of CH at 273 K and 298 K
2
4
(
Figure S10). However, the activated 2 didn’t have any N sorption at 77 K (Figure S11), which
2
is mainly attributed that the framework was collapsed completely after the activation process.
The reason can be confirmed by the PXRD pattern of the activated 2 (Figure S12).
2
Figure 3. The N sorption isotherm of 1 was measured at 77 K. The insert was the pore size distribution.
Catalysis properties.
Due to high BET surface area, multiple pore systems and lots of basic sites, 1 was further studied
its catalytic properties for the Knoevenagel condensation model reaction. The fresh sample was
directly soaked in toluene for one day prior this catalytic reaction. Substrate with different
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structures (0.001 mol) and malononitrile (0.0011 mol) were both added into a glass reactor with
5
mL toluene. When the reaction temperature reached 80 °C, catalytic 1 (0.1 g) was instantly
putted into the reaction solution and stirred at this temperature. The GC instrument was
employed to analyze the yields. Table 2 contains the yield results of all the reactions, including
malononitrile and different aldehyde substrates with or without 1. As illustrated in entry 1 of
Table 2, the final yield of 2−benzylidenemalononitrile is about 97% after reaction 3 hours. The
kinetic catalysis performance of benzaldehyde as substrate was chosen as a model to investigate
the catalytic rate in detail, which illustrated that this reaction almost completed within 3 hours in
the presence of 1 (Figure 4a). Because the corresponding yield almost remained unchanged after
filtering 1 at 40 minute, MOF 1 is clearly necessary for this reaction. Meanwhile, no any
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
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3
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5
5
5
5
5
6
0
1
2
3
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5
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7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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9
0
1
2
3
4
5
6
7
8
9
0
2
−benzylidenemalononitrile can be detected without catalytic 1 after 3 hours in entry 2 and
Figure 4a. In order to investigate the substrate effect, several different substituted aldehyde
reactants were used in the present of 1 under similar conditions. The yields of the aldehyde
substrates with the withdrawing groups (–F and –NO ) were both almost >99% (entries 3 and 4).
2
Whereas, the yield results significantly decreased to 87% for one electron donor –OMe group
(entry 5) and 80% for two –OMe groups (entry 6), respectively.
Table 2 The results of all Knoevenagel condensations.
O
CN
CN
+
R
H
CN
R
CN
Entry
Substrate
Product
Yield (%)
1
2
3
97
4
>99
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>99
87
80
0
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9
0
Furthermore, it is a significant importance issue to recycle the catalysis after reaction. MOF 1
was easily recollected and reused by centrifuging and washing with toluene. The catalytic effect
of recycled 1 was basically no loss after reuse four times. As illustrated in Figure S13, the PXRD
peaks suggested that the framework of recycled samples can keep very well. The results of
FT−IR and TGA of recycle samples after further washing with fresh DMF are similar with the
asꢀsynthesized samples, which illustrates the structure of recycled 1 retained very well (Figures
S14 and S15).
Figure 4. (a) The kinetics results and (b) the recycle performance for this reaction
.
Luminescence properties.
The luminescence behaviors of H BDPO ligand and ground 2 were both investigated in detail.
4
Figure 5a shows the maximum emission of the free ligand at 382 nm under 337 nm. The
resultant 2 showed a significant emission peak at 379 nm under excitation wavelength at 292 nm
(
Figure 5b), revealing that the luminescence property of 2 belongs to the organic ligand. To
study the luminescence detection capability towards NACs, the maximum emission peak of the
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ground samples in DMF with different detectable substances were collected under 292 nm
(Figure 5c). Significantly, it appeared remarkably luminescence quenching behavior in
nitrobenzene (NB) DMF solution. In addition, the luminescence intensity can keep well in DMF
for one day (Figure S16). To further detect the luminescence response, the resultant 2 was
titrated with NB to vary the concentrations (Figure 5d). The corresponding luminescence
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
3
3
3
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4
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0
1
2
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9
0
1
2
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9
0
1
2
3
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7
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9
0
1
2
3
4
5
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9
0
1
2
3
4
5
6
7
8
9
0
−
3
−2
intensity quickly reduced to 81% and 24% at 1 × 10 and 1 × 10 M, respectively, which may
be ascribed to the electron transfer from the host structure of 2 to electronꢀdeficient NB.
Figure 5. The maximum emission and excitation spectra of the free organic ligand (a) and 2 (b). The maximum emission peak of 2 in DMF with
different detectable substances (c) and at different NB concentrations (d).
Hence, the luminescence sensing ability of 2 was further discussed in detail to detect several
typical NACs, including 1,3−dinitrobenzene (1,3−DNB), 2,4−dinitrotoluene (2,4−DNT) and
2,4,6−Trinitrophenol (TNP). The luminescence intensities were monitored with the different
concentration of the analytes in DMF solution (Figures 6a−6c), which almost quenched
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1
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2
2
2
2
2
2
2
2
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completely at last. The quenching efficiency is able to quantitatively determinate by
Stern−Volmer equation as I /I = 1 + K [Q], in which I is the initial intensity without any analyte,
0
sv
0
I is the intensity after treating with the analyte, [Q] is the molar concentration of substances
−
1
0
1
2
3
4
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1
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4
5
6
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8
9
0
(
M ), and K is the Stern−Volmer constant. When (I /I) – 1 vs. [Q] plot exhibits a linear
s
v
0
relationship, the K value can be determine exactly. As shown in Figure S17, the Sterm−Volmer
sv
data for these NACs all close to the linear relationship in the relatively low concentration range.
2
2
3
4
−1
The corresponding K values are 3.0 × 10 , 9.8 × 10 , 1.9 × 10 and 1.2 × 10 M for NB,
sv
1
2
,3−DNB, 2,4−DNT and TNP, respectively. The order of quenching efficiency is TNP >
,4−DNT > 1,3−DNB > NB due to the enhancement of the electron transfer from 2 to NACs
with the increasing amount of nitro groups (Figure 6d). Notably, the UV−Vis result illustrated
that the absorption band of TNP and the emission spectrum of 2 have the most overlap area in
DMF to significantly enhance the quenching effect (Figure S18). In addition, 2 was easily
−
1
recollected by centrifuging 8000 r min for 3 minutes and washed with DMF. As demonstrated
in Figure S19, the luminescence sensing ability of 2 shows a very little change after reusing five
times. Meanwhile, the structure can be keep well after the recycle experiment by the PXRD data
(Figure S20).
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2
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6
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8
9
0
Figure 6. The emission spectra of
2
was titrated in DMF solutions with 1,3−DNB (a), 2,4−DNT (b) and TNP (c), respectively; (d) the
relationships between the maximum emission intensities and the concentrations of NACs.
Selective sensing of antibiotics.
As we known, only few luminescence MOFs have been used as sensors to detect different
[42−49]
antibiotics.
In this work, ten frequently−used antibiotics were selected as models to
investigate the antibiotics detectable ability of 2, including florfenicol (FFC), penicillin (PCL),
thiamphenicol (THI), chloramphenicol (CAP), azithromycin (AZM), sulfamethazine (SMZ),
ronidazole (RDZ), ornidazole (ODZ), nitrofurazone (NFZ) and nitrofurantoin (NFT). The
luminescence data of 2 were detected in the presence of various antibiotics (FFC, PCL, THI,
CAP, AZM, SMZ, RDZ, ODZ, NFZ and NFT) in DMF, demonstrating a clearly luminescence
quenching phenomenon for NFZ or NFT, respectively (Figure 7a). The quenching order of 2
towards these antibiotics is NFT > NFZ > ODZ > RDZ > SMZ > AZM > CAP > THI > PCL >
FFC. The results obviously showed that 2 can be considered as a potential luminescence sensor
to recognize NFZ or NFT via luminescence quenching. In addition, the luminescence response
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2
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2
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2
2
2
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experiments of 2 towards NFZ were measured at different time intervals (Figure 7b). After the
−
5
−5
−1
concentration of NFZ (1.0 ꢀ 10 or 7.0 ꢀ 10 mol L ), the luminescence intensities both
immediately decreased and achieved a minimum value after about 50 s. The intensity further can
be kept for a long time to illustrate that the luminescence intensity can completely quench at a
very short time.
0
1
2
3
4
5
6
7
8
9
0
1
2
3
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1
2
3
4
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9
0
To further investigate the detection ability of 2 towards NFZ or NFT, the titration experiments
were performed by adding NFZ or NFT drop by drop, respectively. With the increasing
concentration of NFZ or NFT, the corresponding luminescence intensity obviously decreased
(Figures 7c and 7d). Meanwhile, the corresponding quenching performance can be quantitatively
determinated by the values of (I /I) − 1 vs the concentrations of NFZ or NFT. As shown in
0
4
4
Figures 7e and 7f, the K values for NFZ and NFT are calculated to be 4.5 × 10 and 4.9 × 10
sv
–
1
2
M with the R values of 0.9989 and 0.9993, respectively. Meanwhile, the recyclability is also a
vital important issue to detect NFZ or NFT. The reused samples were easily recollected and
reused. The recycled crystals can perfectly preserve the luminescence properties like the fresh
samples, which can be further used as a luminescence sensor to redetect NFZ or NFT at least five
times (Figure S21). The integrity of skeleton can be confirmed by PXRD patterns, which can
retain the characteristic peak to prove the stability during the tests (Figure S20). It is significant
work to investigate the luminescence quenching mechanism for NFZ and NFT with high
selectivity of 2. The results illustrated the quenching effect is not trigged by the skeleton broken.
In addition, the quick test results of 2 demonstrated that the quenching effect is also not caused
by guest molecule adsorption. It is easily found that the overlap between the absorption spectra
of NFT or NFZ and the emission spectrum of 2 in DMF from the UV−Vis results (Figure S22),
which illustrated that the excitation energy may be competitively absorbed by the NFZ or NFT
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molecules to obviously reduce the energy transfer to 2 to produce luminescence quenching
phenomenon. All the luminescence data of 2 have been tabularized in Table S2.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
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0
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0
1
2
3
4
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8
9
0
Figure 7 (a) The luminescence intensities of 2 in different antibiotics DMF solutions; (b) the luminescence response rate of 2 in the NFZ at different concentrations;
(c, d) the emission spectra of 2 after titrating with NFT or NFZ; (e, f) the Stern−Volmer plots for the intensity of 2 with different concentrations of NFT or NFZ,
respectively.
CONCLUSION
II
In summary, we have successfully obtained two 3D MOFs. The different metal ions (Co and
II
Zn ) directly generate different structures and properties. The resultant 1 shows high catalysis
effect for the Knoevenagel condensation reaction with outstanding recyclability. In addition, 2
exhibited an excellent luminescence property to use as a fast, recycle, and multi−responsive
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1
1
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1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
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3
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6
luminescence sensor towards TNP, NFZ and NFT, respectively. Further work about novel and
functional MOFs is ongoing in our laboratory.
ASSOCIATED CONTENT
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
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7
8
9
0
1
2
3
4
5
6
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9
0
1
2
3
4
5
6
7
8
9
0
Supporting Information
Electronic Supplementary Information (ESI) available: IR, TGA, PXRD and so on. The
supplementary crystallographic data were deposited with a Cambridge Crystallographic Data
Centre (CCDC) No. 1465197 for 1 and 1580838 for 2.
AUTHOR INFORMATION
Corresponding Author
*
Eꢀmail:
Hongming He: hehongminghz@163.com;
Fuxing Sun: fxsun@jlu.edu.cn
Guangshan Zhu: zhugs@jlu.edu.cn.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
We really thanks to the financial funds from Doctoral Program Foundation of Tianjin Normal
University (043135202ꢀXB1702), Tianjin Science and Technology Fund Project for High
Education (2017KJ127) and NSFC (grant No. 21501064).
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7] Zha, J.; Zhang, X. RoomꢀTemperature Synthesis of TwoꢀDimensional MetalꢀOrganic
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For Table of Contents Use Only
II
II
Two 3D Metal-Organic Frameworks based on Co and Zn clusters for
Knoevenagel Condensation Reaction and Highly Selective Luminescence
Sensing
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*, †
†
*,‡
*,§
Hongming He, QianꢀQian Zhu, Fuxing Sun, and Guangshan Zhu,
Two 3D metalꢀorganic frameworks were successfully synthesized under solvothermal conditions.
CoꢀMOF exhibited highly catalysis effect for Knoevenagel condensation reaction. Meanwhile,
ZnꢀMOF can be served as a fast, recycle, and multiꢀresponsive luminescence sensor towards
TNP, NFZ and NFT, respectively.
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