Synthesis and characterization of a novel o-vanillin schiff base derivatives and their complexes with Zn(II)

Article abstract of DOI:10.1080/15533174.2013.796978

A Schiff base compound (H₂L) was synthesized using o-vanillin and o-phenylenediamine, and then the zinc Schiff base complex was obtained by the reaction of zinc acetate. They were characterized by elemental analysis, the infrared spectroscopy (

Full text of DOI:10.1080/15533174.2013.796978

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Synthesis and Reactivity in Inorganic, Metal-Organic,
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Synthesis and Characterization of a Novel o-Vanillin
Schiff Base Derivatives and Their Complexes With Zn(II)
a
a
a
b
Wen Wu , Yawen Xuan , Jiang Long Yin & Li Shujie
a
Department of Chemistry , Zhou Kou Normal University , He Nan , P. R. China
b
Key Laboratory of Rare Earth Luminescent Material , Zhou Kou Normal University , He
Nan , P. R. China
Accepted author version posted online: 25 Nov 2013.Published online: 25 Feb 2014.
To cite this article: Wen Wu , Yawen Xuan , Jiang Long Yin & Li Shujie (2014) Synthesis and Characterization of a Novel o-
Vanillin Schiff Base Derivatives and Their Complexes With Zn(II), Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, 44:6, 877-880, DOI: 10.1080/15533174.2013.796978
To link to this article: http://dx.doi.org/10.1080/15533174.2013.796978
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 44:877–880, 2014
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2013.796978
Synthesis and Characterization of a Novel o-Vanillin Schiff
Base Derivatives and Their Complexes With Zn(II)
1
1
1
2
Wen Wu, Yawen Xuan, Jiang Long Yin, and Li Shujie
1
Department of Chemistry, Zhou Kou Normal University, He Nan, P. R. China
Key Laboratory of Rare Earth Luminescent Material, Zhou Kou Normal University, He Nan, P. R. China
2
bioinorganic chemistry, catalysis, encapsulation, transport and
L) was synthesized using o-vanillin separation processes, and magnetochemistry.[
11–13]
A Schiff base compound (H
2
and o-phenylenediamine, and then the zinc Schiff base complex
was obtained by the reaction of zinc acetate. They were charac-
terized by elemental analysis, the infrared spectroscopy (IR), ther-
mogravimetric analysis (TG), fluorescence spectrometer (PL), and
antioxidative activity. For Zn(II) complex, fluorescence spectrum
In this article, we report the synthesis and chemical char-
acterization of a novel Zn(II) coordination polymer based
on the new Schiff base ligand (H2L N,N -bis(2-oxy-3-
ꢁ
methoxybenzylidene)-1,2-phenylenediamine), and a kind of
shows that excitation of solid sample at 380 nm produces a strong metallic Schiff base has been synthesized, which is character-
emission with the peak maximum at 596 nm, the ligands display ized by elemental analyses, IR, and thermal gravimetric (TG)
their characteristic emission peaks at 550 nm. The results illustrate
analysis. The luminescence of the complex and the antioxidative
activity are also presented.
that the complex and the ligand inhibition rate were up to 42.55%,
−
1
3
7.27%, respectively, when the concentrations were 10 mg mL .
Keywords fluorescence, Schiff base, Zn(II) compound
EXPERIMENTAL
Physical Measurements
All the starting reagents are of A.R. grade and used as pur-
chased. Elemental analyses (C, H, N) were performed on a Vario
EL III analyzer. Infrared spectra on KBr pellets were recorded on
INTRODUCTION
The considerable attention in designing new coordination
polymers emerges not only from their interesting structural
−1
a Nicolet 5700 spectrophotometer in the range 4000–400 cm
[
1,2]
3]
topologies,
but also from their potential applications in
and the TG runs were taken on a Perkin-Elmer TG-DTA stan-
dard type thermal analysis system. The compound was heated
electronics,[ luminescence, catalysis, magnetism, and
[4]
[5]
[6]
[
7]
molecular recognition. Zinc is the second most abundant tran-
sition metal in the human body, the self-assembly process of
metal complexes of d10 metal ions has grown into a very active
research area, because they exhibit interesting structural fea-
tures and potential applications in light-emitting diodes, gene
expression, apoptosis, enzyme regulation, neurotransmission,
◦
up to 800 C in the atmosphere of nitrogen, at a heating rate of
◦ −1
1
0 C min . The fluorescence spectra was recorded on a model
LS55 spectrofluorimeter (Perkin-Elmer), equipped with a dual
monochromator. The antioxidative activity was performed in
dimethylformamide (DMF) with a Lambda 35 spectrophotome-
ter (Perkin-Elmer).
[
8–10]
fluorescence imaging, and cancer phototherapy.
Schiff base
ligands have played an important role in the development of Synthesis of Ligand (H L) and Polymer
2
coordination chemistry, because they are readily available, ver- Preparation of Ligand (H L)
2
satile and allow a good control over the stereochemistry of the
metallic centers, as well as over the nuclearity of the com-
plexes. These advantages make Schiff bases very good candi-
dates in the effort to synthesize metal complexes of interest in
The synthesis of the ligand is shown in Scheme (1). o-vanillin
(
20 mmol), dissolved in methanol (20 mL), was added drop-
◦
wise with stirring at 60 C to a solution of o-phenylenediamine
(
20.2 mmol) in methanol. The reaction mixture was then cooled
to room temperature. The jaffa orange crystals formed were fil-
tered and washed with 10 mL of acetone. Yield: 65%. Elemental
analysis (%): Anal. Calcd. for C22H20N2O4: C, 70.20; H, 5.36;
N, 7.44; O, 17.0. Found: C, 69.27; H, 5.45; N, 7.48%.
Received 17 March 2013; accepted 11 April 2013.
Address correspondence to Wen Wu, Department of Chemistry,
Zhou Kou Normal University, He Nan 466001, P. R. China. E-mail:
chinawuwen@126.com
Color versions of one or more of the figures in the article can be
found online at www.tandfonline.com/lsrt.
Preparation of the Polymer
The ligand (1 mmol) was dissolved in acetonitrile (5 mL).
After 5 min, 1 mmol Zn(OAC)2·2H2O (1 mmol), dissolved in
877

878
W. WU ET AL.
2
0
8
6
4
2
0
8
6
4
2
0
1
1
1
1
1
SCH. 1. Synthesis of ligand H2L.
methanol (20 mL), was added into the ligand solution, and the
◦
resulting mixture was stirred for approximately 1 h at 60 C. A
4000
3500
3000
2500
2000
1500
1000
500
jaffa orange precipitate was separated from the solution by suc-
tion filtration, purified by washing several times with methanol,
and dried for 2 h in vacuo. Yield: 80%. Elemental analysis (%):
Anal. Calcd. for C22H24N2O7Zn: C, 53.51; H, 4.90; N, 5.67.
Found: C, 53.397; H, 4.81; N, 5.75%.
-1
υ/Αcm
FIG. 1. IR spectra of ligand.
TG Properties
The thermal analysis curve of the studied complex is shown
Hydroxy Radical Scavenging Activity
The hydroxyl radical in aqueous media was generated in Figure 3. There are three main mass loss stages. The first
[
14,15]
◦ ◦
through the Fenton reaction.
The solution of the tested mass loss with 10.2% starts at 105 C and ends at 172 C while
◦
compounds was prepared with DMF. The reaction mixture con- reaching its highest rate at 162 C. The first obvious weight loss
tained 1.0 mL 0.05 M Tris-HCl buffer (pH 4.1), 1.0 mL 0.1 mmol was attributed to the loss of three H O (calcd. about 10.7%). In
2
−1
−1
L
methyl violet, 1.0 mL 0.5 mmol L FeSO4, 0.50 mL 3% compound, the last two obvious weight loss stages with 74.55%
H2O2, and 0.5 mL tested compound solution. The sample with- starts at 207 C and ends at 593 C, which is related to the de-
out the tested compound was used as the control. Absorbances composition of the Schiff base ligands. The residues are 16.7%
◦
◦
(
Ai, A0, A) at 576 nm were measured. The suppression ratio (calcd. about 16.5%) of the total mass. And at the same time
for HO· was calculated from the following expression: Sup- certain types of polymers formed in the residues.
pression ratio η = [(Ai − A0)/(A − A0)] × 100%, where Ai is
the absorbance in the presence of the tested compound; A0 is Luminescent Spectrum
the absorbance in the absence of the tested compound; A is the
The fluorescence properties of the Schiff base ligand and
absorbance in the absence of the tested compound, FeSO4 and its Zn(II) complex were studied at room temperature in the
H2O2.
solid state (Figure 4). The complex exhibits weak fluorescence
in comparison to the ligands. For Zn(II) complex, excitation
of solid sample at 380 nm produces a strong emission with
the peak maximum at 596 nm. The ligands display their char-
acteristic emission peaks at 550 nm. Since the Zn(II) ion is
RESULTS AND DISCUSSION
IR Spectra
In the free ligands, Figure 1 clearly shows that the band of
349 cm was observed in IR spectra and assigned to ν(O-
H) absorption, the strong band at 1615 was due to vC=N of
imine, which indicated that the Schiff base ligands had been
obtained. The IR spectra of the ligand and the corresponding
complex Zn(II) were very similar (Figure 2). In metal complex
−1
22
3
2
1
1
1
1
0
8
6
4
2
[
Zn(L)2], azomethine band (vC=N) was shifted to lower frequen-
−1
10
8
cies (1602 cm ) after complexation. This lower shift could be
attributed to a weakening of the C=N bonds on adduct forma-
tion and this can be explained by the donation of electrons from
6
[
16]
4
nitrogen to the empty d-orbitals of the transition metal ions.
−1
2
The strong bands at 1298 and 1236 cm in the free Schiff base
ligands were due to the phenolic C O stretchings. On complex
formation, these bands are shifted to lower frequencies (1196
and 1183 cm ) indicating coordinations through the phenolic
oxygens.
0
4
000
3500
3000
2500
2000
-1
υ/cm
1500
1000
500
−1
FIG. 2. Infrared spectra of the zinc polymer.

o-VANILLIN SCHIFF BASE DERIVATIVES AND THEIR COMPLEXES
879
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
4
3
2
ligand
coordination polymer
4
41
40
39
38
37
36
35
34
33
32
31
0
100
200
300
400
500
600
700
800
900
2
4
6
8
10
Concentration (mg/mL)
Temp./ć
FIG. 3. The TG curves of polymer.
FIG. 5. The ligand and its complex suppression ratio for OH.
difficult to oxidize or reduce due to its stable d10 configuration. that the complex and the ligand inhibition rates were up to
Thus, the emission observed in the complexes is tentatively 42.55%, 37.27%, respectively, when the concentrations were
∗
[17,18]
−1
assigned to the π −π intra ligand fluorescence.
It is inter- 10 mg mL . It is clearly shown that metal complex exhibits
1
esting that the Zn(II) complexes show a lower intensity emission more considerable scavenging activity than the ligand. There-
originating from metal-centered metal-to-ligand charge transfer/ fore, the scavenging effect of the complex studied in o-vanillin
ligand-to-metal charge transfer (MLCT/LMCT) than that of the Schiff base should be further investigated.
free ligand. Metal ions may quench the fluorescence emission of
some Schiff base ligands containing an aromatic ring. Quench-
ing of fluorescence of a ligand by transition metal ions during
CONCLUSION
In conclusion, the Zn(II) complex and the ligand each dis-
plays intense fluorescence at room temperature. It is suggested
that the compounds exhibit the potential for use in applications
as photochromatism materials. Furthermore, our results suggest
that the scavenging effect of the complex increases with in-
complexation is a rather common phenomenon that is explained
by processes, such as magnetic perturbation, redox activity, elec-
tronic energy transfer, etc.
[
19–21]
Antioxidative Activity
The suppression ratios of the ligand and its complex for OH· creasing complex concentration. Metal complex exhibits more
radical are shown in Figure 5. The results show that the lig- considerable scavenging activity than the ligand.
and and complex can not only scavenge OH·, but also increase
with increasing complex concentration. The research indicated
FUNDING
This work was supported by the Foundation of He’nan Ed-
ucational Committee [Grant No. 2009B430017; 13A150103]
and Department of science and technology (Grant No.
32102310296). We thank the Foundation of Zhoukou Normal
University key Laboratory of rare earth luminescent material for
financial support of this research(Grant No: K201319).
600
500
400
300
200
100
0
ligand
1
SUPPLEMENTAL MATERIAL
Supplemental data for this article can be accessed on the
publisher’s website.
polymer
460 480 500 520 540 560 580 600 620 640 660
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