34 卷 7 期
2015. 7
结
构 化 学 （JIEGOU HUAXUE）
Chinese J. Struct. Chem.
Vol. 34, No. 7
1099─1106
Zinc Complexes Based on Organochalcogen
Ligand Mbit: Syntheses, Structures
and Photocatalytic Properties①
JIA Wei-Guo② DAI Yuan-Chen LI Dan-Dan
WANG Dong-Sheng SHENG En-Hong②
(College of Chemistry and Materials Science, Center for Nano Science and
Technology, The Key Laboratory of Functional Molecular Solids, Ministry of Education,
Anhui Laboratory of Molecular-based Materials, Anhui Normal University, Wuhu 241000, China)
ABSTRACT The zinc complex with neutral organochalcogen ligand Mbit, [(Mbit)2Zn](ClO4)2 (1,
Mbit = 1,1΄-methylenebis(3-methyl-imidazole-2-thione)), has been synthesized and characterized.
The complex has been characterized by elemental analysis, NMR and IR spectra. The molecular
structure of 1 has been determined by X-ray crystallography. For the complex, C18H24Cl2N8O8S4Zn,
Mr = 744.96, triclinic, space group P 1 , a = 11.2923(18), b = 11.9353(19), c = 13.837(3) Å, α =
114.763(2), β = 92.132(2), γ = 116.039(2)°, V = 1464.6(5) Å3, Z = 2, Dc = 1.689 g/cm3, λ = 1.54184
Å, μ = 1.363 mm-1, F(000) = 760, S = 1.098, the final R = 0.0554 and wR = 0.0.1579. Complex 1
exhibits photocatalytic activity for methyl orange (MO) degradation under UV light and shows good
stability toward photocatalysis.
Keywords: zinc, organochalcogen, structure, photocatalytic;
DOI: 10.14102/j.cnki.0254-5861.2011-0597
complexes with sulfur-rich ligands, to the best of our
1 INTRODUCTION
knowledge, analogue neutral organochalcogen
Transition metal complexes with softer sulfur-rich
ligands derived from imidazole are least studied.
ligands, for example, neutral organochalcogen li-
Therefore, the synthesis of transition metal com-
gand, B-centerd anionic bidentate ligand bis(mer-
plexes with neutral organochalcogen ligands is very
R
captoimidazolyl)hydroborate (Bm ) and tridentate
R
attractive from the coordination chemistry and
ligand tris(mercaptoimidazoly)hydroborate (Tm )
application points of view, and the complexes
systems, have attracted considerable attention due to
containing these functional groups strongly bound to
their widespread applications and ability to form
transition metal are of considerable interest. Many
diverse coordination network architectures in the
complexes have been synthesized and characterized
[1]
past decades . B-centered ligands systems have
in the past decades[7], and zinc complexes have
been extensively investigated by many research
found widespread applications in inorganic che-
[2-6]
groups
, however, among these transition metal
mistry[8-10]. We have reported the nickel and iridium
Received 8 December 2014; accepted 2 June 2015 (CCDC 979000)
① This work was financially supported by the National Natural Science Foundation of China (21102004),
National Training Programs of Innovation and Entrepreneurship for Undergraduates (201410370040), and
Training Programs of Innovation and Entrepreneurship of Anhui Province for Undergraduates (AH201410370040)
② Corresponding authors. E-mail: [email protected] and [email protected]
JIA W. G. et al.: Zinc Complexes Based on Organochalcogen
Ligand Mbit: Syntheses, Structures and Photocatalytic Properties
1100
No. 7
complexes with orchanochalcogen ligands exhibit
was obtained by filtration and washed with MeOH
high and moderate activities for addition-polyme-
(2×1 mL) and dried in vacuo for 15 h. Recrystalli-
[11, 12]
. Orcha-
zation of the product from CH3CN/Et2O afforded
nochalcogen chemistry revolving transition metal
white crystals (148 mg, 40% yield). 1H NMR (300
complexes is one of the research focuses of our
MHz, CD3CN): δ (ppm) = 3.39 (s, 2CH3, 6H), 6.41
group, and we seek to discover new transition metal
(s, CH2, 2H), 7.29 (d, imidazole, 2H), 7.57 (d,
complexes and hope to exploit their chemistry in a
imidazole, 2H);
variety of potential applications.
(ppm) = 36.89 (CH3), 59.44 (CH2), 121.65
rization of norbornene, respectively
13
C NMR (300 MHz, CD3CN): δ
In order to understand the chemistry of zinc
(imidazole), 124.36 (imidazole), 152.91 (C=S). Anal.
complexes containing organochalcogen ligand and
Calcd. for C18H24Cl2N8O8S4Zn: C, 29.02; H, 3.25; N,
their potential applications, we report herein an
15.04%. Found: C, 28.96; H, 3.50; N, 15.26%. IR
facile route to the synthesis of a novel zinc complex
(KBr cm-1): 521(w), 625(m), 676(w), 762(m),
with Mbit ligand [(Mbit)2Zn](ClO4)2 (1). In addition,
1115(s), 1236(m), 1321(s), 1398(m), 1472(m),
complex 1 exhibits photocatalytic activity for methyl
1578(m), 3130(m), 3169(m).
orange degradation under UV light and shows good
2. 3
stability toward photocatalysis.
Photocatalytic activity study
The photocatalytic activities of the samples were
evaluated by the degradation of MO in an aqueous
2
solution. 40 mL of a MO aqueous solution with a
EXPERIMENTAL
concentration of 10-5 M was mixed with 20 mg of
2. 1
the catalysts and was then exposed to illumination.
Materials and methods
All manipulations were carried out under nitrogen
Before turning on the lamp, the suspension con-
using standard Schlenk and vacuum-line techniques.
taining MO and the photocatalyst was magnetically
All solvents were purified and degassed by standard
stirred in dark conditions for 30 min until an
procedures. The starting materials, Mbit and 2, were
adsorption-desorption equilibrium was established.
synthesized according to the procedures described in
Samples were then removed regularly from the
[7, 13]
. 1-Methylimidazole was purchased
reactor and centrifuged immediately to separate any
from Acros. All the other reagents were com-
suspended solid. The transparent solution was
literatures
1
13
mercially available and used as received. H and C
analyzed by a UV-vis spectrometer. A 300 W me-
NMR spectra were obtained via a Bruker DMX-300
dium pressure mercury lamp served as a UV light
spectrophotometer in CD3CN, using TMS as an
source. The Langmuir-Hinshelwood equation (r0 =
internal standard for all compounds. Elemental
k0C0/1 + K0C0) was employed to quantify the
analyses were performed on an Elementar III vario
degradation reaction of MO (r0 is the initial rate, k0
EI Analyzer. IR spectra were recorded on a Niclolet
represents the kinetic rate constant and K0 shows the
AVATAR-360 IR spectrometer. The UV light source
adsorption coefficient of the reactant MO). As the
was a 300 W high-pressure mercury lamp.
value of C0 is too small, K0C0 ≪ 1 and the L-H rate
2. 2
Synthesis of [(Mbit)2Zn](ClO4)2 (1)
expression can be simplified to a first-order rate
Mbit (0.24 g, 1 mmol) was dissolved in 5 mL
expression: r0 = dC0/dt = k0C0. This equation can be
dichloromethane. A solution of Zn(ClO4)2·6H2O
solved to obtain ln(C/C0) = −k0t. Based on the
(0.186 g, 0.5 mmol) in 5 mL MeOH was added
Lambert-Beer law, C/C0 = I/I0 and therefore the
dropwise to the stirring solution of Mbit. The
equation can finally be reduced to ln(I/I0) = −k0t.
mixture was stirred for 8 h under an atmosphere of
2. 4
Structure determination
nitrogen, resulting in the formation of a colorless
A colourless crystal of 1 with dimensions of
solution and a white precipitate. This white product
0.20mm × 0.18mm × 0.15mm was selected for
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构
学（JIEGOU HUAXUE）Chinese
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J.
Struct. Chem.
1101
X-ray diffraction analysis. The X-ray diffraction data
MeOH/CH2Cl2 solvents and isolated in pure form
were collected using a Bruker Smart CCD diffrac-
as a white solid at room temperature (Scheme 1).
tometer with graphite-monochromated MoKα radia-
The zinc complex 1 was fully characterized by
tion (λ = 0.71073 Å). A total of 5084 reflections
elemental analysis, IR and NMR spectroscopies.
were collected in the range of 1.68≤θ≤25.0° (–13
The formation of 1 is conformed by the
≤h≤12, –14≤k≤14, –16≤l≤16), including 4163
appearance of 1H signals at 3.39, 6.41, 7.29 and
independent ones with Rint = 0.0259. All the data
7.57 ppm, which can be assigned to methyl, CH2,
were collected at room temperature and the struc-
and two imidazolyl hydrogens of the Mbit ligand,
tures were solved by direct methods with SHELXS-
respectively. 1H NMR data for the complex are
97[14] and subsequently refined on F2 by using full-
qualitatively very similar to those of the free
[15]
matrix least-squares techniques (SHELXL-97)
,
ligand, with only modest upfield chemical shifts
were appli-
observed for the hydrogen in free ligand.
ed to the data. The final refinement gave R = 0.0554
Likewise, upfield shifts of up to 10.6 ppm for the
[16]
and SADABS absorption corrections
2
2
2
and wR = 0.1579 (w = 1/[σ (Fo ) + (0.0473P) +
8.7169P], where P =
(Fo2
+
2Fc2)/3),
(Δ/σ)max =
3
0.000, (Δρ)max = 0.911 and (Δρ)min = –0.392 e/Å .
thione carbons in their
13
C NMR were measured
upon complexation to the zinc metal. The complex is thermally robust, air-stable solid, only
sparingly soluble in MeOH but more so in MeCN,
DMSO and DMF. The IR spectrum of 1 in the
3 RESULTS AND DISCUSSION
solid state exhibited intense N-C-N and C=S
3. 1
stretching at about 1578, 1236 and 1115 cm-1,
Synthesis of the complex
[(Mbit)2Zn](ClO4)2 (1) was obtained by reacting
Zn(ClO4)2 with
Mbit
(1:2
ratio)
respectively.
in
2+
N
N
N
N
2
N
N
S
S
N
+
S
Zn(ClO4)2·6H2O
S
N
Zn
S
N
(ClO4)2
S
N
Mbit
N
N
1
Scheme 1.
Synthesis of complex 1
3. 2 Crystal structure of [(Mbit)2Zn](ClO4)2 (1)
Crystal suitable for X-ray crystallography of 1
was obtained by slow diffusion of diethyl ether
Table 1.
Bond
into concentrated solution of the complex in
acetonitrile solution. The selected bond lengths
and bond angles are shown in Table 1.
Selected Bond Lengths (Å) and Bond Angles (°)
Dist.
Bond
Dist.
Bond
Dist.
Zn(1)–S(1)
2.3224(17)
Zn(1)–S(2)
2.3646(17)
Zn(1)–S(3)
2.3743(17)
Zn(1)–S(4)
2.3235(17)
S(1)–C(2)
1.713(6)
S(2)–C(6)
1.715(6)
S(3)–C(11)
1.709(6)
S(4)–C(15)
1.716(6)
Angle
(°)
Angle
(°)
Angle
(°)
S(1)–Zn(1)–S(2)
108.90(7)
S(1)–Zn(1)–S(3)
108.43(6)
S(1)–Zn(1)–S(4)
115.16(6)
S(2)–Zn(1)–S(3)
108.33(7)
S(2)–Zn(1)–S(4)
109.32(6)
S(3)–Zn(1)–S(4)
106.49(7)
JIA W. G. et al.: Zinc Complexes Based on Organochalcogen
Ligand Mbit: Syntheses, Structures and Photocatalytic Properties
1102
No. 7
The structure of 1 is solved in the triclinic
first-principles DFT computations were per-
crystal system and P 1 space group. As shown in
Fig. 1, the coordination geometry of the central
formed by using the projector-augmented plane
zinc center can be best described as a distorted
interaction as implemented in the Vienna ab initio
tetrahedron with four S atoms, like the structure
simulation package (VASP)[22]. The calculated
of the closely related zinc complex Zn[BmR]2[6].
electronic structure demonstrates that band gaps
The Zn–S bond lengths in [(Mbit)2Zn](ClO4)2
of two zinc complexes are 2.47 eV for complex 1
(average = 2.3462 Å) are marginally longer than
and 3.21 eV for complex 2, which are smaller
Me
those in Zn[Bm ]2 (average = 2.337 Å)
[17]
wave (PAW)[21] method to model the ion-electron
, and
than the experimental values (3.97 and 4.08 eV),
shorter than other Bm derivatives of zinc com-
as shown in Fig. 3. This deviation is caused by
R
Bu
[18]
plexes including [Tm ]ZnBr
[19]
and [Zn(Tm)Cl]
(average = 2.3586 and 2.357 Å, respectively).
the fact that the DFT-PBE method tends to
underestimate the band gap[23].
However, they are within the narrow range
20
2.32～2.37 Å found in a variety of zinc thione
16
complexes[20]. In order to know the zinc com-
12
plexes with sulfur-rich ligands fully, and under-
(a hv)
2
complex 1
complex 2
8
stand the difference between the neutral and ionic
sulfur-rich ligands, complex Zn[Bmme]2 (Bmme =
4
bis(2-mercapto-1-methylimidazolyl)hydrobo) (2)
0
was obtained according to the literature proce-
2
3.97
4
4.08
5
Band gap (eV)
dure using Zn(OAc)2 and BmMe compound as the
starting materials[17].
3
Fig. 2.
Band gap determination of complexes 1 and 2
To study the photocatalytic activity of zinc complexes in details, we select methylene orange (MO),
which is chemically stable and poorly biodegradable
dye, as a model of dye contaminant to evaluate the
photocatalytic effectiveness in the purification of
wastewater. The experiments were performed in
typical processes. A suspension containing 1 (20 mg)
and 40 mL of MO (3.0×10−5 mol·L−1) solution was
stirred in the dark for about 30 min. Then, the
mixture was stirred continuously under UV irradiaFig. 1. Crystal structure of [(Mbit) 2Zn]+ anion.
All hydrogen atoms are omitted for clarity
tion from a 300 W high-pressure mercury lamp. A
sample solution (3 mL) was taken every 20 min and
separated through centrifuge to remove suspended
3. 3
Photocatalytic properties of zinc complexes
catalysts, while the starting point did not contain the
The band gaps of zinc complexes 1 and 2 were
first 30 min to rule out the effect of its absorption on
measured by a solid state UV-vis diffuse reflec-
the catalyst surfaces. After filtration, the samples
tion measurement method at room temperature.
were analyzed by the UV-vis spectrophotometry. By
The results showed that the band gaps were 3.97
contrast, the simple photolysis experiment was also
eV for complex 1 and 4.08 eV for complex 2 (Fig. 2),
completed under the same conditions without any
respectively, which implied their potential can-
catalyst. The organic dye concentrations were esti-
didate as a photocatalyst. Meanwhile, the
mated by the absorbance at 464 nm (MO).
2015
Vol. 34
结
构
学（JIEGOU HUAXUE）Chinese
化
Fig. 3.
J.
Struct. Chem.
1103
Band structures of complexes 1 and 2
As illustrated in Figs. 4 and 5, the absorption
activities for the degradation of MO than 2. The
peaks of MO decreased obviously under UV in the
possible reason maybe lies in the difference of
presence of complex 1, while the absorption peaks
components and band gaps. Interestingly, appro-
decreased much slowly in the presence of complex 2.
ximately 16% of MO has been decomposed during
In addition, changes in the concentration of MO
the first 40 min, which indicates that complex 1 has
solution under UV were plotted versus irradiation
a high photocatalytic activity for the degradation of
time. The results show that the MO degrades
MO. However, in the visible light region, it displays
approximately from 100% to 80% for complex 1,
no effects on the decomposition of MO because
and to 10% for complex 2 during 140 minutes. It is
complex 1 can not be excited by visible light.
obvious that complex 1 has higher photocatalytic
1.0
0.8
C/C0
0.6
0.4
without catalyst
with catalyst 1
with catalyst 2
with complex1 and TEMPO
0.2
0.0
0
20
40
60
80
100
120
140
Irradiation time/min
Fig. 4.
Photocatalytic degradation of MO solution under UV with the use of complex 1; the black curve is the control
experiment without any catalyst; the green curve is the photocatalytic degradation of MO solution under
UV with the use of complex 2. The red curve is the control experiment with the catalyst 1 and TEMPO
0min
20min
40min
60min
80min
100min
120min
140min
A
350
400
450
500
550
600
Wavelength/nm
(a)
(b)
Fig. 5. (a) UV-Vis absorption spectra of MO solution degraded by complex 1 after the UV-visible light irradiation
for different time intervals. (b) Photograph showing the photocatalytic degradation under UV-visible
light for 0, 20, 40, 60, 80, 100, 120 and 140 min (from left to right, respectively)
JIA W. G. et al.: Zinc Complexes Based on Organochalcogen
Ligand Mbit: Syntheses, Structures and Photocatalytic Properties
1104
No. 7
The stability and reusability of the photocatalyst
of each powder were basically identical to those of
were further evaluated in the presence of complex 1
the parent compounds, indicating that this complex
for the degradation of MO. In each test, the photo-
is stable during photocatalysis of MO (Fig. 6). Fig. 7
catalyst was reused after washing with deionized
shows that the photocatalyst of complex 1 exhibited
water while other factors were kept the same. The
effective catalytic performance for the degradation
results indicate that compound 1 has a high
of MO during four consecutive cycles. The MO
photocatalytic activity for the degradation of MO.
degrades activities approximately 90.6%, 89.8% and
Additionaly, the powders were obtained by filtration
88.2%, respectively.
after photocatalytic reaction, and the PXRD patterns
10
20
30
40
50
60
70
T w o theta
Fig. 6. Powder XRD patterns of complex 1 (black), after a first recycle photocatalysis process (red);
after a second recycle photocatalysis process (green); after a third recycle photocatalysis process (blue)
1.0
0.906
0.898
0.882
2
3
Degradation efficiency %
0.8
0.6
0.4
0.2
0.0
1
R ecycle Tim es
Fig. 7.
Cycling runs in the photocatalytic degradation of MO over complex 1
To study the photocatalytic reaction mechanism,
irradiation under UV light, electrons (e-) in the
the photodegradation of MO was carried out in the
valence band (VB) were excited to the conduction
presence of 2,2,6,6-tetramethylpiperidine 1-oxyl free
band (CB), and holes (h+) were left in VB. Then O2
radical (TEMPO), a widely used radical scaven-
was reduced into O2- by the combination of electrons
ger[24]. The presence of TEMPO depressed the photo-
(e-), which further turned into ·OH. At the same time,
degradation of MO, which suggests that the photo-
the interaction of holes (h+) with OH− may produce
degradation of MO is predominately through the
a ·OH which is well known to have high activity to
[25]
attacking of ·OH radicals
. The possible photo-
catalytic mechanism is proposed as follows: During
destroy the MO.
2015
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结
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J.
Struct. Chem.
1105
crystallographic confirmed the structures of zinc
CONCLUSION
complex 1. In addition, complex 1 exhibits photoIn conclusion, we have reported a novel zinc
catalytic activity for methyl orange degradation
complex with neutral organochalcogen Mbit ligand.
under UV light and shows good stability toward
A combination of spectroscopic studies and X-ray
photocatalysis.
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