Silver(I)-Based Complexes Used as High-Performance Photocatalysts for the Degradation of Organic Dyes in Water

Article abstract of DOI:10.1002/ejic.201900026

Coordination compounds have been used as efficient photocatalysts for the degradation of pollutive organic dyes due to their semiconductive nature and diverse structures that may be adjusted by the central metals and ligands. Herein we prepared N′,N′-2,2-tetrakis(diphenylphosphanylmethyl)thiocarbohydrazide (tpptch) and utilized it to react with AgX (X = Br, I, CN) in different solvent systems. These reactions afforded two dicationic tetranuclear complexes {[Ag₄X₂(tpptch)₂]X₂ (1: X = Br; 2: X = I)}, one 1D coordination polymer [Ag₂I₂(tpptch)]_n (3) and one neutral tetranuclear complex [Ag₄(CN)₂(dptpptch)₂] (4, dptpptch is the anion of deprotonated tpptch after an enolization). In 1–4, the S atom of the C=S group binds at one Ag^I atom in 1 or 2, or remains uncoordinated in 3, or connects with two Ag^I atoms after transforming into the C–S^– end in 4. The catalytic activities of these compounds toward the photodegradation of nine organic dyes under UV irradiation were examined, among which 3 showed the best performance. Their anodic photocurrent responses and HOMO–LUMO energy gaps derived from density functional theory (DFT) calculations correlated well with the photocatalytic activities. The different bindings of the S end of tpptch and dptpptch ligands with Ag^I centers in 2–4 may be contributed to the discrepancy in their catalytic activities. The results provide a ready route to design and prepare highly stable and efficient photocatalysts for treating dye-polluted water.

Full text of DOI:10.1002/ejic.201900026

A Journal of
Accepted Article
Title: Silver(I)-Based Complexes Used as High-Performance
Photocatalysts for the Degradation of Organic Dyes in Water
Authors: Chao-Fan Liu, Chun-Yu Liu, Zhi-Gang Ren, and Jian-Ping
Lang
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201900026
Link to VoR: http://dx.doi.org/10.1002/ejic.201900026

European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
Silver(I)-Based Complexes Used as High-Performance
Photocatalysts for the Degradation of Organic Dyes in Water
†
[a]
†[a]
*[a]
*[ab]
Chao-Fan Liu, Chun-Yu Liu, Zhi-Gang Ren and Jian-Ping Lang
-
Abstract: Coordination compounds have been used as efficient
photocatalysts for the degradation of pollutive organic dyes due to
their semiconductive nature and diverse structures that may be
adjusted by the central metals and ligands. Herein we prepared
N',N'-2,2-tetrakis(diphenylphosphanylmethyl)thiocarbohydrazide
transforming into the C–S end in 4. The catalytic activities of these
compounds toward the photodegradation of nine organic dyes under
UV irradiation were examined, among which 3 held the best
performance. Their anodic photocurrent responses and HOMO–
LUMO energy gaps derived from density function theory (DFT)
calculations correlated well with the photocatalytic activieties. The
different bindings of the S end of tpptch and dptpptch ligands with
Ag(I) centres in 2-4 may be contributed to the discrepancy in their
catalytic activities. The results provide a ready route to design and
prepare highly stable and efficient photocatalysts for treating dye-
polluted water.
(tpptch) and utilized it to react with AgX (X = Br, I, CN) in different
solvent systems. These reactions afforded two dicationic
tetranuclear complexes ([Ag
4
X
2
(tpptch)
2
]X
(tpptch)]
2
(dptpptch) ] (4, dptpptch is the
2
(1: X = Br; 2: X = I), one
1
D coordination polymer [Ag
2
I
2
n
(3) and one neutural
tetranuclear complex [Ag
4
(CN)
2
anion of deprotonated tpptch after an enolization). In 1-4, the S
atom of the C=S group binds at one Ag(I) atom in 1 or 2, or remains
uncoordinated in 3, or connects with two Ag(I) atoms after
Introduction
4 3 4 n 4 3 4
{[Ag (NO ) ](dpppda)} . It consists of chair-like [Ag (NO ) ]
cluster cores bridged by dpppda ligands and exhibited good
photocatalytic performance in the degradation of
In recent years, various coordination compounds are
employed as photocatalysts for decomposing and removing
a series of pollutants including nitroaromatics,
nitrobenzene
(
NB), p-nitrophenol
(
PNP
)
and 2,4-
[
1,2]
[9]
polycyclic
dinitrophenol (DNP). For two P-N hybrid ligands N-
diphenylphosphanylmethyl-3-aminopyridine(3-dppmapy)
[
3]
[4]
[23]
aromatic hydrocarbons (PAHs), organic pesticides and
[
5,6]
dyes
in aqueous phase due to their semiconductive
and
(3-bdppmapy),
{[Ag
bdppmapy)
irregular [Ag
N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine
[25]
nature, accurate measurable structures and easy synthesis
and modification.
coordination compounds, Ag nanoparticles (NPs) and Ag
nanocomposites (NCs) are known for their stable and fine-
tuning structures with semiconductive nature and prominent
photocatalytic properties.
group of strong electron donors that have been widely used
in the formation and stabilization of Ag(I) complexes.
their reactions with AgNO
3
gave rise to
{[Ag (NO ](3-
respectively. Both compounds have the
] and cyclic [Ag (NO ] cluster cores
[
7,8]
[23]
Silver-containing substances like Ag(I)
2
(NO
3
)
2
](dppmapy)
}
2 n
and
4
3 4
)
[
9]
[25]
2 n
} ,
4
(NO
)
3 4
2
3 2
)
and were found not stable enough toward UV irradiation in
water and thus not suitable for the photocatalysis. However,
[
10-19]
Phosphine ligands are a
[
23]
{[Ag
bdppmapy) }
2
(Sal)
2
](dppmapy)
}
2 n
and
4 4
{[Ag (Sal) ](3-
[
20,21]
[25]
2 n
(Sal: salicylate) were stable and showed
Recently, we have investigated the photocatalytic
degradation capabilities of some multinuclear Ag-P
coordination complexes. The adjustment of the structures of
Ag(I) coordination compounds with phosphine ligands has
been adequately performed by employing different Ag(I)
sources such as AgX (X: halide/pseudohalide) and Ag(Ox)
good photocatalytic activities toward decomposing some
dyes such as rhodamine B (RhB), eriochrome black T
(EBT), acid black (AB) and nigrosin (NO). These results
revealed that combination of other donor atoms into the
multidentate phosphine ligands may exert great impact not
only on the cluster core structures of Ag(I) coordination
compounds, but also on their stabilities and activities during
the photocatalysis reactions.
[
22,23]
(
Ox: oxysalt).
Apart from Ag(I) sources, we have also diverted our
attention on modifying the phosphine ligands by controlling
the number of phosphine ends and introducing other donors. Cu, resulting in the formation of many polynuclear metal
[
26,27]
[28]
Sulfur atom displays good affinity for Au,
Ag and
[
29]
[
24]
Some tetraphosphine (P4) ligands
nitrogen (P-N) hybrid ligands
and phosphine-
have been designed and
employed to assemble with Ag(I) salts. For example, the
assembly of P4 ligand 1,4-N,N,Nʹ,Nʹ-
tetra(diphenylphosphanylmethyl)benzene diamine (dpppda)
with AgNO resulted in 1D coordination polymer
complexes with unique fluorescence and photocatalysis
[
25]
[30]
properties.
How to combine P and S donor atoms
together into polynuclear metal complexes has received
[
31,32]
a
much interest.
Two synthetic strategies are available.
[
33]
[34]
One is to introduce extra S source such as H
2
S, Na
into the reaction system in the presence of
phosphine ligands. The other is to incorporate S in-between
2
S,
[
35]
3
a
thiophenol
[
36]
the P donors in a hybrid ligand. Previously, we prepared
P-S hybrid ligand N,N-
bis(diphenylphosphanylmethyl)aminothiocarbamide
[a]
Chao-Fan Liu, Chun-Yu Liu, Dr. Zhi-Gang Ren, Prof. Jian-Ping
Lang, College of Chemistry, Chemical Engineering and Materials
Science, Soochow University, Suzhou 215123, Jiangsu, P. R.
China.
a
(dppatc), whose Au(I) complexes showed good
photocatalytic activities toward the degradation of
E-mail: jplang@suda.edu.cn, renzhigang@suda.edu.cn
http://lmdc.suda.edu.cn/
[37]
nitroaromatics in water.
[
b]
†]
Prof. Jian-Ping Lang, State Key Laboratory of Organometallic
Chemistry, Shanghai Institute of Organic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, P. R. China
These authors contribute equally to this work.
Although the P-S hybrid ligands could be prepared with
various S sources and readily coordinated to coinage
metals, it is uneasy to control the coordination mode of the
S atom. Actually, the binding modes of most phosphine
[
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/ejic.xxxxxxxxx
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European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
ligands are hardly alterable, which limits the structure
diversity of the resulting complexes. We herein prepared a
new
tetrakis(diphenylphosphanylmethyl)thiocarbohydrazide
tpptch) (Scheme 1), which has a thiocarbonyl group
P-S
hybrid
ligand,
N',N'-2,2-
(
symmetrically embedded in a tetraphosphine environment.
Notably, tpptch could be transformed into dptpptch
through an enolization and deprotonation process. Thus, its
-
C=S bond was turned into C–S (Figure S1 in the
Supporting Information), and this S atom displayed several
coordination modes. With tpptch in hand, we isolated four
Ag(I)/tpptch complexes and used three of them as
photocatalysts for the photodegradation of nine organic
dyes including eriochrome black T (EBT), malachite green
(MG), sunset yellow (SY), orange I (OI), orange II (OII), acid
black (AB), amaranth red (AR), methyl blue (MB) and
methyl orange (MO). Their photocurrent responses and
photocatalytic performances largely depended on the S
coordination and could be rationalized by the differences of
their HOMO–LUMO energy gaps derived from density
function theory (DFT) calculations.
Scheme 2. Reactions of tpptch with AgBr, AgI and AgCN.
The ligand tpptch and
air and moisture. tpptch is readily soluble in common
solvents such as CH Cl , CHCl , MeCN, DMF and DMSO,
moderately soluble in MeOH and EtOH, but insoluble in
water. Compounds are insoluble in water and common
organic solvents. The elemental analyses of tpptch and
were consistent with their chemical formulas. In their IR
1-4 are relatively stable toward
2
2
3
1-4
Scheme 1. Synthesis of tpptch.
1-4
-1
spectra, bands at 1480, 1432, 845, 739, 694 cm were
attributed to the phenyl groups. In , the characteristic band
Results and Discussion
4
-
-1
for CN appeared at 2112 cm . The ESI-MS (positive-ion in
MeOH) of tpptch: m/z = 921.2608 ([tpptch+Na] ) (Figure
+
Synthetic and Spectral Aspects
S2) showed the ligand could have good stability in solvents.
1
The H NMR spectrum of tpptch in CD
showed the signals for the -CH
2
2
Cl
- (3.44, 3.67 and 3.82 ppm),
-NH- (7.03 and 7.73 ppm) and phenyl groups (7.58-7.09
2
(Figure S3)
The ligand tpptch was prepared as a white crystalline
[
38]
powder in 83% yield by Mannich reaction by refluxing the
mixture containing thiocarbohydrazide, diphenylphosphine
and a slight excess (10 mol%) of formaldehyde in benzene
31
ppm), respectively. The P{H} NMR spectrum of the ligand
in CD Cl (Figure S5) also has two peaks at -27.83 and -
2
2
for 9 h. Compounds
or 69% yield ( ) by the reactions of tpptch with 2 equiv. of
AgBr in MeOH or AgI in MeCN at room temperature
followed by diffusion of Et O or i-PrOH, respectively
Scheme 2). Other attempts including changing the molar
ratios of reactants or using other solvents also produced
and in lower yields. We also carried out the reactions of
tpptch with AgCl or AgSCN in CH Cl to produce only
1
and
2
were isolated in 34% yield (
1
)
27.92 ppm, respectively. The division of the peaks of -NH-
group in H NMR and the P signals in the P{H} NMR
indicated the different environments of the two -NH- groups.
1
31
2
2
However, the NMRs for
their poor solubility in organic solvents. The PXRD patterns
for matched well with those generated from their single-
crystal data (Figure S6). Thermogravimetric analyses (TGA)
of (Figure S7) revealed that they were all stable under
200 °C. The structures of tpptch (Figure S8) and were
1-4 could not be measured due to
(
1
1-4
2
2
2
1-4
some white solids, which were insoluble in common organic
solvents and also excluded their structural characterization.
Intriguingly, introduction of pyridine or DMF into the reaction
1-4
established by single-crystal X-ray diffraction analyses.
system of AgI and tpptch afforded
yield, respectively. Addition of pyridine or DMF to the
reaction system of did not yield any other isolable
3 in 33% yield and 26%
Crystal Structures
1
compounds. When tpptch was used to react with AgCN, a
proton from one –NH group of tpptch could be taken away
Compounds
crystallize in the triclinic group Pī and monoclinic group
P2 /c, respectively. Their structures are quite similar, and
only the structure of the dication of is presented in Figure
. This dication contains two [Ag
1
·MeOH
and
2·2i-PrOH·4MeCN
-
-
by CN due to the stronger basicity of CN . Accompanied
1
-
with an enolization transition process, the C–S end of the
2
2+
resulting dptpptch anion was then generated, which was
1
2
(tpptch)] units, which
further caught by Ag centres to form
4 in 36% yield.
are joined together by two Ag–μ-I–Ag connections and two
Ag–S bonds. The two Ag atoms are trigonally and
tetrahedrally coordinated. The four P ends of tpptch bind
[
39]
two Ag atoms in a side-by-side coordination mode,
as
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European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
each –N(CH
2
PPh
)
2 2
end offers one –PPh
2
group to chelate
Compound
4
·2MeCN·2MeOH crystallizes in the triclinic
one Ag centre.
group Pī. The structure of
two [Ag (CN)(dptpptch)] units via two Ag–S bonds (Figure
). The Ag atoms are tetrahedrally and trigonally
coordinated, respectively. The coordination modes of the
four P ends are the same to those in and . The S atom
bridges two Ag atoms from two [Ag (CN)(dptpptch)] units.
The lengths of the bonds connected to the S atoms in
4 may be viewed as being built of
2
3
1
2
2
4
support our speculation that tpptch was deprotonated to
yield the dptpptch anion via an enolization transition where
-
the C=S end was transformed into a C–S end. The C–S
bond length (1.751(3) Å) in
of the C=S bonds in (1.688(8) Å in
and 1.675(5) Å in ) and tpptch (1.691(3) Å), and is close
to the C–S single bond in [(AgPPh (o-mpspa)] (1.7701(66)
Å, mpspa = 3-methoxyphenyl-2-sulfanylpropenoato).
, two C–N bonds linking the thiocarbonyl group are
similar (1.328(6) ~ 1.353(6) Å) and in the range of single
bonds. In , C1–N2 (1.288(4) Å) is obviously shorter than
C1–N1 (1.382(4) Å), suggesting a double bond nature.
The mean Ag–S length (2.6026(10) Å) in is in-between
that in (2.612(2) Å) or (2.6264(15) Å) and that in
Ag (dppatc) ](NO ·2MeOH (2.4378(9) Å).
4
is evidently longer than those
1
-3
1
, 1.689(5) Å in
2
3
3 2
)
[
40]
In
2
+
Figure 1. View of the [Ag
4
(tpptch)
2
I
2
]
dication in 2·2i-PrOH·4MeCN. All H
1-3
atoms are omitted for clarity. Symmetry code for A: -x + 1, -y + 1, -z + 1.
4
[
41]
4
1
2
[42]
[
2
2
3 2
)
Optical Properties
The solid-state UV-Vis absorption spectra of tpptch
(Figure S10) showed that these compounds have
good adsorptions at UV region. Their band energy gaps (E
and 1-4
g
)
[43]
were obtained by the Kubelka-Munk method
:
Figure 2. View of a section of the 1D chain in 3·1.5MeCN. All H atoms and
solvent molecules are omitted for clarity. Symmetry code for A: -x + 0.5, y +
E = 1240/λ
0
.5, -z + 0.5.
2
F = (1-R) /2R
(
λ: wavelength, R: reflectance at a given energy),based on
their solid-state diffusion-reflection data (Figure 4) which
were estimated to be 3.18 3.51 eV. The E values (< 3.6
Compound
3
·1.5MeCN crystallizes in the monoclinic
2+
group P2
1 2
/n. The aforementioned [Ag (tpptch)] unit is
~
g
also observed in
for the four P ends of tpptch is similar to those in
though its C=S bond remains intact. Each Ag is
tetrahedrally coordinated by two pairs of P and μ-I atoms. I2
binds the two Ag atoms within the [Ag
I1 bridges the [Ag
3
(Figure 2), and the coordination mode
and 2,
eV) indicated they are of semiconductive nature, and may
be potential photocatalysts for the treatment of pollutants in
water.
1
[
9]
2+
2
(
tpptch)] unit, while
+
2
I(tpptch)] units, thus forming a 1D chain
extending along the b axis.
Figure 4. Diffuse reflectance UV-Vis spectra of Kubelka-Munk functions
versus energy (eV) for 1-4 and tpptch.
Figure 3. Molecular structure of 4. All H atoms and solvent molecules are
omitted for clarity. Symmetry code for A: -x + 1, -y + 1, -z + 1.
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European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
Photocurrent Responses
0
c = c - kt
where k is the apparent zero-order rate constant. The fitted
The stabilities of
1
-4
in water toward UV light were
lines were generated by the least-squares method with
evaluated by detecting the concentrations of the dissolved
Ag from their suspensions (each of them contains 10 mg
catalyst and 15 mL water, by ICP technique) after 12 h of
slopes of –k/c
0
. The k values were calculated to be 8.00 ×
+
-3
-3
-3
-3
10 (EBT), 5.90 × 10 (MG), 4.90 × 10 (SY), 4.10 × 10
-3
-3
-3
(
OI), 4.59 × 10
(OII), 3.88 × 10
(
AB), 3.71× 10
(
AR),
[
22]
-3
-4
-1
-1
stirring and irradiation. The decomposed percentage of
are 1.58 ( ), 0.27 ( ), 0.33 ( ) and 0.28 ( ) (mol%),
respectively, implying that are suitable for the
photocurrent measurements and UV photodegradation
experiments. The photocurrent responses of tpptch and
were examined under xenon light irradiation, employing a
1
-
1.29 × 10
(
MB) and 1.33 × 10
(MO) mol L min ,
4
1
2
3
2-4
4
respectively. The reactions following the zero-order kinetics
implied that the above degradation might take place at the
[
9]
surface of 2.
2
-
4
manual shutter to block the irradiation (shutter interval: 20
s). According to the cyclic voltammetry experiments (Figure
S11), the bias potential (0.80 V vs. SCE) was restricted in
[
25]
the range of the anodic reactions. As shown in Figure 5,
tpptch and generated steady anodic photocurrents
of 2.4 μA, 5.1 μA, 9.2 μA and 3.5 μA, respectively. Among
the three catalysts, possesses the highest photocurrent
while has the lowest, which is consistent with their E
values. There was barely any attenuation for 2-4 after
,
2
,
3
4
3
4
g
[
22,25]
ten cycles of UV light on/off. The PXRD patterns of these
samples after photocurrent experiments (Figure S12)
indicated that
2-4 remained steady, and they could hold
satisfactory stability in the following photodegradation
[
22,25]
reactions
Figure 6. Time-dependent concentrations of dyes in water catalyzed by 2
under UV irradiation. The fitted lines were generated by the least-squares
method.
Controlled experiments on the photodegradation of
EBT were carried out to study the influences of light and the
catalyst. (Figures
7
and S14 (in the Supporting
2
Information)). Under the catalysis of
2
(BET surface 10.3 m
-1
g ) (Figure S15a), the degradation of EBT could be
accomplished in 120 min with UV irradiation, but was quite
slow (14.5% within 240 min) in the dark, implying the UV
irradiation was indispensable in the EBT degradation. In the
cases of no catalyst and the known photocatalyst nano-TiO
2
2
-1
(
25 nm, BET surface area = 80.5 m g ) (Figure S15b), the
EBT degradation was found to be 26.7% and 63.3% after
40 min’s irradiation. Therefore, was more efficient than
nano-TiO with a larger BET surface area.
2
2
2
Figure 5. Photocurrent responses of ITO electrodes coated with tpptch
(
black), 2 (blue), 3 (green) and 4 (red) with UV irradiation being turned on and
-1
2 4
off. Conditions: bias 0.80 V, vs. SCE, [Na SO ] = 0.1 mol L .
Photocatalytic Properties
Compound 2 was selected as the model catalyst to examine
the photodegradation of different dyes as it hold the best stability,
highest yield and medium
photocatalytic properties of 2 toward nine common organic dyes
EBT, MG, SY, OI, OII, AB, AR, MB and MO) under UV
E
g
value among 1-4. The
(
-
2
irradiation (365 nm, 40 mW cm ) were shown in Figures 6 and
S13 (in the Supporting Information). Most dyes (EBT, MG, SY,
OI, OII, AB and AR) could be efficiently decomposed within 120-
Figure 7. Time-dependent concentrations of EBT in water under different
conditions.
270 min. However, degrading MB and MO took much longer
time under the same conditions.
The degradation of each dye using
2 followed a zero-
order kinetics which can be expressed by:
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European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
The photoactivity and stability of
2
during the EBT
3 2 2
by weighing BaCO (after absorbing CO by Ba(OH) ) (in
degradation were examined by reusing it as the catalyst
separated by centrifugalization and then mixed with a new
portion of EBT aqueous solution followed by UV irradiation)
for 5 rounds. As shown in Figure 8, there has no obvious
decay of the catalytic performance after 5 cycles as EBT
was steadily degraded in each single experiment.
the Supporting Information) and the ion chromatography (IC)
+
-
2-
(
on NH
Information).
and SO
4
, NO
3
9,37]
and SO
4
ions (Table S1, in the Supporting
Under the catalysis of , the yields of CO
(Table 1) were over 90%, which was consistent
with the above-mentioned UV-Vis results. The amounts of
[
2
2
2-
4
+
4
-
the resulting NH
implying that some N groups were likely turned into N
and NO
3
ions were somewhat low,
, as
Furthermore, the PXRD patterns of
matched well with those of the as-synthesized
S16), suggesting that was stable during the catalysis.
2
after each recycle
2
[
50,51]
2
(Figure
suggested in the literatures.
2
+
-
2-
Table 1. Yields (%) of CO
2
,
NH
4
,
NO
3
and SO
4
for the
photodegradation of EBT, MG and SY catalyzed by 2.
Products
CO
EBT
93.0
12.4
29.7
92.4
MG
94.3
9.3
26.5
-
SY
2
92.1
9.0
+
NH
4
-
NO
3
31.8
91.1
2
-
SO
4
The photocatalytic activities of 2, 3 and 4 were presented in
Figure. 9 and Figure S18 (in the Supporting Information). The
orders of the degradation rates were similar (EBT > MG > SY)
when different catalysts were employed. Compound 3 took
approximately 100 min (EBT), 120 min (MG) and 160 min (SY)
to break down these dyes to the extent of 90%, while 2 took 120
min (EBT), 150 min (MG) and 180 min (SY) to reach the same
extent. The photodegradation of these dyes using 4 as a catalyst
was much slower and needed 180 min (EBT), 250 min (MG) and
more than 360 min (SY) to reach 90% decomposition. Therefore,
the catalytic activities of 2-4 followed the 3 > 2 > 4 order.
Figure 8. Recycled photocatalytic behaviour of 2 for decomposing EBT in
water under UV light.
The possible mechanism for the above photocatalysis
was assumed to be the ·OH radical-mediated route (Figure
[
44,45]
S17a),
excited electrons (e ) and left holes (h ), and gave rise to
the formation of ·OH radicals by their reactions with O and
O, respectively. The advanced oxidation process (AOP)
of the ·OH radicals decomposed the dyes into CO , H
This mechanism
during which the irradiation on the catalyst
−
+
2
H
2
2
2
O
[
46,47]
and other less harmful substance.
[
22]
was verified by a method reported previously. When tert-
butyl alcohol (TBA, 0.2 mL) was introduced as the ·OH
radical scavenger
system containing
[
48]
into the photodegradation reaction
2
and EBT, only 5.8% of EBT was
degraded within 3 h, implying that most ·OH radicals were
captured by TBA and thus the degradation reaction was
blocked (Figure S17b). On the other hand, in order to prove
the ·OH radicals’ formation, terephthalic acid was
[
49]
introduced as the capture agent of ·OH radicals into the
above system to produce 2-hydroxyterephthalic acid. As
–3
–1
shown in Figure S17c, when a NaOH (2 × 10 mol L )
solution containing terephthalic acid and was irradiated by
UV light, the photoluminescent (PL) response of the
resulting 2-hydroxyterephthalic acid was observed at 425
nm. And its PL intensity was gradually increased when the
UV irradiation time was prolonged (Figure S17d). However,
2
Figure 9. Time-dependent concentrations of EBT, MG and SY in water
catalyzed by 2, 3 and 4 under UV irradiation.
Considering that the C=S group remains intact in 3 and
binds at one Ag(I) atom in 2, but gets deprotonated and
there was no obvious increase of PL without
2. These
-
results revealed that the above photodegradation would
transformed to C–S that links two Ag(I) atoms in 4, we assume
[22]
be ·OH radical-mediated oxidation reaction.
Since EBT MG and SY are readily degraded, they
that importing the S donor atoms into the Ag(I) structures might
play a negative effect on their photocatalytic performances. The
tighter binding of S with Ag atoms, the poorer catalytic activities
the complexes exhibited. This assumption agreed with our
previous hypothesis that the Ag(I) clusters were the active
,
were used as model substrates to examine the
photodegradation products. The mass conservations of C,
N and S elements after the UV irradiation were measured
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
[
22,23,25]
centres for the photocatalyst,
and that the number of Ag(I)
In order to rationalize their different photocurrent
responses and photocatalytic capabilities, we performed the
DFT calculations on the B3LYP level (Figure S19) to
determine the HOMO, LUMO and HOMO−LUMO (H−L)
atoms and their coordination modes may influence the catalytic
activities.
A comparasion on the photocatalytic performances of 3 and
some other reported photocatalysts towards the degradation of
different organic dyes was listed in Table 2. The catalytic
[
63]
energy gaps of
2
-4
(Table 3). The H-L gaps
3 < 2 < 4
were in good agreement with the E
g
values obtained from
performance of 3 was better than those of [Ag
and 4NDc towards the degradation of EBT, comparable to those
of Pt-In /BiVO and Sn-doped TiO towards the dgradation of
MG, but somewhat worse than those of {[Pb(Tab) (PF and
HRPm/LbL towards the degradation of SY. In addition, 3 may
not be a suitable photocatalyst for the decomposition of MB and
MO when compared with those Zn(II), Cu(II) and Pb(II)
complexes.
4
I
4
(3-bdppmapy)
2
]
n
the UV-Vis diffuse reflectance data. Under the UV
irradiation, the exciting of electrons from HOMO to LUMO
+
O
2 3
4
2
may help the separation of electron-hole (h ) and electrons
-
]
2 2
) }
6 4 n
(e ), which may lead to the increasing of the anodic
[
25]
current. To this end,
value, showed the largest photocurrent. The catalytic
activity order was also in line with the sequences
of the E and photocurrent values, which might be related to
the easier generation of hydroxyl radicals (·OH) for lower E
3, having the lowest H-L gap and E
g
3
> 2 > 4
g
g
materials under UV irradiation, and was essential to the
degradation of organic dyes in water under this mechanism
involving ·OH radical intermediates.
[
25]
Table 2. Efficiencies of some photocatalysts towards the degradation of
different organic dyes.
Organic Time
Efficiency Ref.
(%)
[
a]
Photocatalysts
Ag (3-bdppmapy)
NDc
Pt-In
Sn-doped TiO
[Pb(Tab)
HRPm/LbL
[Cd (btbb)(bptc)(H
Zn (dpcpbe) (BET)0.5(μ
Cu(3-dpye)(1,3-BDC)]·3H
dyes
EBT
EBT
MG
(min)
150
210
40
Conclusions
[
4
I
4
2
]
n
~95
~40
100
22
52
53
4
In this article, we have demonstrated that the as-
synthesized P-S hybrid ligand tpptch displayed a versatile
reactivity toward silver halide and pseudohalide salts. Three
2
O
3
/BiVO
4
2
MG
SY
340
80
100
100
44
86
32
80
13
65
54
55
56
57
58
59
60
61
{
2 2 6 4 n
] (PF ) }
SY
60
tetranuclear complexes (
1, 2 and 4) and one 1D CP (3)
{
2
2
O)]·4H
2
O}
n
MB
MB
MB
MO
MO
140
90
240
150
120
were successfully prepared and characterized. The S
4
2
3
-OH)
2
(H
2
O)
2+
atoms in the [Ag
coordinated to one Ag(I) atom from their equivalent unit,
and the S atoms do not coordinate to any Ag atom in . The
ligand tpptch in is transformed into dptpptch via an
2
(tpptch)] unit of 1 and 2 are only
[
2
O
Pb
[
2
(ttt)(ox)0.5(H
O(2,6-
2
O)
Zn
4
3
NDC)
3
2 2
(DMF)1.5(H O)0.5]·4DMF·7.5H O
4
[
[
[
b]
b]
b]
{
{
[Cu(btmx)
[Cu(btmx)
2
(H
(Cl)
2
O)]·2NO
]·5H O}
3
}
n
MO
MO
MO
EBT
MG
SY
140
140
140
120
150
180
80
56
81
96
99
96
62
enolization process, which turns the C=S bond into the C–
2
2
2
n
-
S bond under basic conditions, and each S links two
2 n
[Cu(btmx)(Cl) ]
3
This
work
different Ag atoms. Compounds 2, 3 and 4 held sustained
stability in water under UV light, and exhibited good
catalytic activity toward the photodegradation of several
[
a] 3-bdppmapy = N,N-bis(diphenylphosphanylmethyl)-3-aminopyridine; NDc =
N-doped TiO coating; Tab = 4-(trimethylammonio)benzenethiol; HRPm/LbL =
micro-encapsulated layer-by-layer horseradish peroxidase; btbb = 1,4-bis(2-(4-
thiazolyl)benzimidazol-1-ylmethyl)benzene; H bptc = 3,3’,4,4’-benzophenone
tetracarboxylic acid; dpcpbe (3,5-dicarboxyl-phenyl)-(4-(2’-carboxyl-
phenyl)-benzyl)ether; BET = 1,1’-(2’-oxybis(ethane-2,1-diyl))bis(1,2,4-triazol-1-
yl); 3-dpye = N,N’-bis(3-pyridinecarboxamide)-1,2-ethane; 1,3-H BDC = 1,3-
benzenedicarboxylic acid; ttt 1,3,5-triazine-2,4,6-triyltrithio-triacetic acid;
ox = oxalic acid; 2,6-NDC = 2,6-naphthalenedicarboxylate; btmx = 1,4-
bis(1,2,4-triazole-1-methylene)-2,3,5,6-tetramethyl benzene
b] visible light (xenon arc lamp), in the presence of H
organic dyes including EBT
Compound , which possesses the highest stability, could
be recycled 5 times in the photodegradation without
obvious catalytic activity decay. Compound showed the
, MG, SY, OI, OII, AB and AR.
2
2
4
H
3
=
3
best performance not only in its dye photodegradation, but
also in its photocurrent response. These results provide us
a good insight into the relationship between the structure
2
=
H
2
(especially the coordination mode of S atom) and the
[
2 2
O .
catalytic activity of the complex. It is anticipated that rational
assembly of Ag(I) salts with other P-S hybrid ligands could
produce more Ag(I)-based compounds with more
fascinating frameworks and much better performances in
advancing optoelectronic responses and treating polluted
water.
Table 3. HOMO, LUMO and HOMO-LUMO (H-L) energy gaps of tpptch
and 2-4 calculated with the DFT method.
Compounds
HOMO
energy (eV)
(H)
LUMO
energy (eV)
(H)
H-L energy gap
(eV)
Experimental Section
tpptch
-5.38
-4.69
-4.21
-4.50
-1.31
-1.33
-1.52
-1.08
4.07
3.36
2.69
3.42
2
3
4
General Procedures: All chemicals were obtained from
commercial sources and used as received. The elemental
analyses (EA) of C, H, N and S were carried out on a Vario
Micro cube organic elemental analyzer. Powder X-ray
diffraction (PXRD) patterns were collected on a PANalytical
Aeris diffractometer (Cu-Kα). Other analytical instruments
involved in this article were the same as those used in our
[
22]
previous works unless otherwise noted.
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
Synthesis of tpptch. A benzene suspension (50 mL)
1481(m), 1432 (s), 1242 (m), 1184 (m), 1099 (s), 1027 (m),
998 (w), 740 (s), 694 (s).
containing HPPh
2
(2.50 g, 13.4 mmol), thiocarbohydrazide
(0.36 g, 3.4 mmol) and paraformaldehyde (0.40 g, 13.3
mmol) was refluxed under nitrogen atmosphere for 9 h and
then cooled to ambient temperature. The resulting mixture
was concentrated by rotary evaporation, leaving a crude
X-Ray Structure Determinations: Crystallographic data of
tpptch·2CH
2 2
Cl , 1·MeOH, 2·2i-PrOH·4MeCN, 3·1.5MeCN, and
4·2MeCN·2MeOH were collected on a Bruker D8 QUEST X-ray
oily product. It was then re-crystallized in CH
The colourless crystals of tpptch·2CH Cl was collected by
filtration, washed with methanol and dried in vacuo. Yield:
2 2
Cl and MeOH. diffractometer by using graphite monochromated Mo-Kα (λ =
2
2
0.71073 Å) radiation. Absorption corrections (multi-scan),
Lorentz and polarization effects corrections were applied. The
2
2
.52
g
2
(83% based on HPPh ). Anal. Calcd. for
structures were solved by direct methods and refined on F by
C
53
H
50
N
4
P
4
S (tpptch): C, 70.81; H, 5.61; N, 6.23; S, 3.57.
full-matrix least-squares methods with SHELXTL-2016 program
[
64]
-
Found: C, 70.43; H, 5.65; N, 6.31; S, 3.58 (%). IR (KBr disk,
cm ): 1511(s), 1480(s), 1432(s), 1243 (m), 1157 (m),
package.
In 1·MeOH, one free Br was disordered over four
-1
close positions with occupancies 0.5/0.3/0.1/0.1. The MeOH
solvent molecule was disordered over two positions with equal
occupancies, while some other disordered solvents were treated
as a diffuse contribution to the overall scattering without specific
1
1
4
095(s), 1026(m), 845(m), 739(s), 694(s); H NMR (CD
00 MHz, ppm): δ 7.73 (s, 1H, -NH), 7.58-7.09 (m, 40H, -
), 3.67
2 2
Cl ,
Ph), 7.03 (s, 1H,-NH), 3.82 (d, J = 13.1 Hz, 2H, -CH
2
13
[65]
(
(
1
5
d, J = 12.8 Hz, 2H, -CH
151 MHz, CD Cl , ppm): δ 180.38, 133.60, 133.11, 129.44,
29.29, 129.36-128.62, 128.62-128.34, 61.56, 61.20, 54.20,
2
), 3.44 (s, 4H, -CH
2
); C NMR
atom positions by the SQUEEZE routine of PLATON. In 2·2i-
PrOH·4MeCN, the i-PrOH solvent molecule was disordered over
two positions with equal occupancies. In 4·2MeCN·2MeOH, the
MeCN and MeOH molecules were disordered over two and
three positions, respectively with occupancies 0.6/0.4 and
2
2
31
1
2 2
4.02, 53.84, 53.66, 53.48; P{ H} NMR (243 MHz, CD Cl ,
ppm): δ -27.88.
0.5/0.3/0.2. All non-hydrogen atoms except for the disordered
Synthesis of [Ag
4
Br
2
(tpptch)
2
]Br
2
(1). A MeOH (5 mL)
ones were refined anisotropically. The H atoms of the disordered
MeOH and i-PrOH in 1·MeOH and 2·2i-PrOH·4MeCN were not
located, while all other H atoms were assigned in geometrically
idealized positions and constrained to ride on their parent atoms.
A summary of pertinent crystallographic data for these crystals is
listed in Table S2 while selected bond lengths and angles are
listed in Table S3.
suspension of AgBr (0.016 g, 0.08 mmol) and tpptch
0.036 g, 0.04 mmol) was stirred in the dark at ambient
temperature. The suspension became colourless and clear
after 2 h, and was then slowly layered with Et O. ·MeOH
(
2
1
was formed as colourless block crystals after 7 days. The
solvated MeOH was then removed under vacuum. Yield for
1
C
:
106
0.017
g
Br
(34% based on Ag). Anal. Calcd. for
: C, 49.95; H, 3.95; N, 4.40%. Found:
CCDC 1881789-1881793 for 1·MeOH, 2·2i-PrOH·4MeCN,
H100Ag
4
4 8
N P
8
S
2
3
2 2
·1.5MeCN, 4·2MeCN·2MeOH and tpptch·2CH Cl ,. These
C, 49.36; H, 4.01; N, 4.25%. IR (KBr disk): 3617 (m), 3253
data can be obtained free of charge from the Cambridge
Crystallographic Data Centre.
(
(
m), 3049 (m), 2790 (m), 1628 (m), 1531 (s), 1434 (s), 1159
m), 1096 (m), 1026 (w), 998 (w), 892 (w), 739 (s), 695 (s).
Synthesis of [Ag
4 2 2 2
I (tpptch) ]I (2). A mixture containing tpptch
Photocurrent
and
Photocatalytic
Activity
(0.036 g, 0.04 mmol) and AgI (0.019 g, 0.08 mmol) in MeCN (5
Measurements: The photocurrent responses tests were
measured on a CHI-630E electrochemistry workstation in a
three-electrode system. The working electrode 2 was
prepared on a clean ITO glass (10 Ω/sq) with 0.49 cm (0.7
cm × 0.7 cm) effective area by coating well ground powder
samples mixed with Nafion-D521. The reference electrode
and the auxiliary electrode were saturated calomel
electrode (SCE) and platinum electrode, respectively. A
mL) was stirred in the dark at ambient temperature, which turned
colourless and clear after 2 h, and was then slowly layered with
i-PrOH. Colourless blocks of 2·2i-PrOH·4MeCN were formed
after 5 days. The solvated MeCN and i-PrOH were removed
under vacuum. Yield for 2: 0.038 g (69% based on Ag). Anal.
4 4 8 8 2
Calcd. for C106H100Ag I N P S : C, 46.52; H, 3.68; N, 4.09.
Found: C, 47.11; H, 3.86; N, 4.18 (%). IR (KBr disk): 3181 (m),
-1
3
1
049 (m), 1621 (m), 1482 (s), 1434 (s), 1219 (w), 1185 (w),
096 (m), 1026 (m), 998 (w), 855 (m), 739 (s), 692 (s).
2 4
Na SO aqueous solution (0.1 mol L , 100 mL) in a quartz
cuboid container (5 cm × 5 cm × 5.5 cm) was used as the
electrolyte solution. The distance between the UV light
source (a xenon lamp, equipped with a UV-transmitting filter,
Synthesis of [Ag
2
I
2
(tpptch)]
0.036 g, 0.04 mmol), AgI (0.019 g, 0.08 mmol) and MeCN
5 mL) was stirred for 2 h, to which was then added 1 mL of
n
(3). A mixture of tpptch
(
(
365 nm, radiation output: 50 W, UV output: 6.6 W) and the
working electrode was set as 20 cm. The photocatalytic
activities of the catalysts were studied under the irradiation
pyridine and kept stirring for another 2 h. After layering onto
the solution by Et O for 7 days, the colourless blocks of
·1.5MeCN were formed, and desolvated under vacuum.
-2
2
of a mercury lamp (400 W, 365 nm, 40 mW cm ). A
suspension containing 30 mL of an organic dye (EBT MG
MB or MO) (0.1 g L ) in water and 20
mg of a well-ground powder of each catalyst was stirred
and exposed to the UV light irradiation. A UV-Vis
spectrophotometer was used to detect the remaining
percentage of each dye (c/c , c and c are the initial and the
3
,
,
-1
Yield for
C H50Ag I N P
53 2 2 4 4
4
3
: 18 mg (33% based on Ag). Anal. Calcd. for
S: C, 46.52; H, 3.68; N, 4.09. Found: C,
7.06; H, 3.96 (%); N, 4.28. IR (KBr disk): 3617 (m), 3253
SY, OI, OII, AB, AR,
(
(
m), 3049 (m), 2790 (m), 1628 (m), 1531 (s), 1434 (s), 1157
m), 1096 (m), 1026 (w), 998 (w), 892 (w), 739(s), 695 (s).
0
0
remaining concentrations of the dye) through monitoring its
characteristic absorption band (530 nm for EBT, 425 nm for
MG, 481 nm for SY, 476 nm for OI, 485 nm for OII, 620 nm
for AB, 523 nm for AR, nm for MB and 465 nm for MO).
Synthesis of [Ag
of ·2MeCN·2MeOH were obtained in an analogous
manner described in the preparation of by using tpptch
0.036 g, 0.04 mmol) and AgCN (0.011 g, 0.08 mmol) in a
4 2 2
(CN) (dptpptch) ] (4). Colourless blocks
4
1
(
mixed solution of MeCN (2.5 mL) and MeOH (2.5 mL). The
solvated MeOH and MeCN were removed under vacuum.
Computational Methods: The HOMO and LUMO energies
of tpptch and 2-4 were calculated with B3LYP functional by
using their crystal structure data. LanL2DZ relativistic
effective core potential and the 6-31G(d,p) basis set were
used for Ag and other atoms, respectively. All calculations
Yield for
4
: 0.017 g (36% based on Ag). Anal. Calcd. for
: C, 56.91; H, 4.33; N, 6.14. Found: C,
7.12; H, 4.79; N, 6.19 (%). IR (KBr disk): 3046 (m), 2958
w), 2845(w), 2112(m), 1637(w), 1617 (m), 1538 (s),
C
5
(
108 4 10 8 2
H98Ag N P S
This article is protected by copyright. All rights reserved.

European Journal of Inorganic Chemistry
10.1002/ejic.201900026
FULL PAPER
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Several Ag(I)-P-S
Ag-P-S Photocatalysts
complexes are assembled
and exhibited high
photocurrent responses and
excellent photochemical
performance in degrading
organic dyes in water.
†
[ a]
Chao-Fan Liu,
Liu,
Chun-Yu
†
[ a]
* [a]
Zhi-Gang Ren and
*
[ab]
Jian-Ping Lang
Page No. – Page No.
Silver(I)-Based Complexes
Used as High-Performance
Photocatalysts for the
Degradation of Organic
Dyes in Water
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