A series of organic-inorganic hybrid materials consisting of flexible organic amine modified polyoxomolybdates: synthesis, structures and properties

Article abstract of DOI:10.1039/c6ra21603j

A series of organic-inorganic hybrid complexes based on different types of polyoxomolybdates and transition metal complexes, namely, [Zn₂(TPMA)₂(H₂P₂Mo₅O₂₃)]·11H₂O (1), [Zn₂(TPMA)₂(Mo₈O₂₆)] (2), [Co₂(TPMA)₂(Mo₈O₂₆)] (3), [Ni₂(TPMA)₂(Mo₈O₂₆)(H₂O)₂] (4), [Ni₂(TPMA)₂(2-PA)(H₂O)](PMo₁₂O₄₀) (5) [Cu₂(TPMA)₂(Mo₈O₂₆)] (6), 2[Cu(TPMA)(CrMo₆(OH)₆O₁₈)]·H[Cu₂(TPMA)₂(CrMo₆(OH)₆O₁₈)]·4H₂O (7) (TPMA = Tris[(2-pyridyl)methyl]amine, 2-PA = 2-picolinic acid), have been successfully synthesized under hydrothermal conditions. All complexes were characterized by single-crystal X-ray structural analysis, powder X-ray diffraction, IR spectroscopy and TG analysis. All the complexes showed polyoxomolybdate-based zero-dimensional (0D) structures, and could be further extended into three-dimensional (3D) supramolecular frameworks through hydrogen bonding interactions. In addition, the electrochemical properties of complexes 1-7 have been investigated. Interestingly, some complexes have efficient photocatalytic activities to degradate pararosaniline hydrochloride dye molecules.

Full text of DOI:10.1039/c6ra21603j

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DOI: 10.1039/C6RA21603J
Journal Name
ARTICLE
A Series of Organic–inorganic Hybrid Materials Consisting of
Flexible Organic Amine Modified Polyoxomolybdates: Synthesis,
Structures and Properties
Received 00th January 20xx,
Accepted 00th January 20xx
a
Chunhua Gonga, Xianghua Zenga, Chengfeng Zhua Jiahui Shua, Pingxiu Xiaoa, Hao Xua, Lichun Liu∗,
, ,
DOI: 10.1039/x0xx00000x
,b
a,c
Junyong Zhanga, Qingdao Zeng∗ , Jingli Xie∗
www.rsc.org/
A series of organic–inorganic hybrid complexes based on different types of polyoxomolybdates and transition metal
complexes, namely, [Zn2(TPMA)2(H2P2Mo5O23)]·11H2O (1), [Zn2(TPMA)2(Mo8O26)] (2), [Co2(TPMA)2(Mo8O26)]
[Ni2(TPMA)2(Mo8O26)(H2O)2] (4), [Ni2(TPMA)2(2–PA)(H2O)](PMo12O40 (5) [Cu2(TPMA)2(Mo8O26)]
(3),
(6),
)
2[Cu(TPMA)(CrMo6(OH)6O18)]·H[Cu2(TPMA)2(CrMo6(OH)6O18)]·4H2O (7) (TPMA = tris[(2–pyridyl)methyl]amine, 2–PA = 2–
picolinic acid), have been successfully synthesized under hydrothermal conditions. All complexes were characterized by
single–crystal X–ray structural analysis, powder X–ray diffraction, IR Spectroscopy and TG analysis. All the complexes
shown polyoxomolybdates–based zero–dimensional (0D) structures, and could be further extended into three–
dimensional (3D) supramolecular frameworks through hydrogen bondings interactions. In addition, the electrochemical
properties of complexes 1–7 have been investigated. Interestingly, some complexes have efficient photocatalytic activities
to
degradate
Pararosanline
Hydrochloride
dye
molecule.
Introduction
The development of multifunctional polyoxometalates represents such as metal ions, organic ligands, solvent, pH and temperature.
one of the enduring challenges in the field of organic-inorganic Therefore, the optimal selection of metal ions and organic ligands
1
hybrid materials. As discrete molybdenum oxide clusters with plays a key role for the design and synthesis of corresponding
structural and compositional diversities, polyoxomolybdates include functional organic–inorganic hybrid materials.
isopolyoxomolybdates and heteropolyoxomolybdates, such as
Even though there are numerous examples in the syntheses of
diverse organic–inorganic hybrid materials by controlling the pH
3–
[Mo6O19]2–, 2 [Mo7O24]6–, 3 [Mo8O26]4–, 4 [P2Mo5O23]6–, 5 [PMo12O40
]
6
3– 7
]
13
14
15
,
[CrMo6(OH)6O18
and so on. These polyoxomolybdates have a value,
reaction temperature,
reaction time,
synthesis
16
number of terminal and bridging O atoms, and can be modified by technologies
and so on, it is anticipated that more specific
different metal ions and organic ligands to form organic–inorganic crystalline materials could be achieved by systematically studying
8
hybrid materials. As such, the hybrid materials have the dual the experimental parameters and reaction mechanism of these
characteristics of polyoxomolybdates and organic molecules and synthetic processes could be elucidated to some extent. To explore
consequently, they received considerable attention due to their intriguing variety of architecture of hybrid materials, chemists have
9
10
multi–functional properties, such as magnetism,
catalysis,
embarked on the combination of different transition metal
11
12
molecular recognition,
electrochemical activity.
However, to complexes with POMs cluster, and already got some novel
17
date, it still remains a challenge to rational synthesize organic– structures. Obviously, this strategy could synthesize a variety of
inorganic hybrid materials because of a variety of variable factors organic-inorganic hybrid materials incorporating different POM
systems.
In the previous literature reports, multidentate flexible ligands
a.
tris[(2–pyridyl)methyl]amine (TPMA) and their derivatives chelated
College of Biological, Chemical Science and Engineering, Jiaxing University,
Jiaxing 314001, P. R. China E-mail: jlxie@mail.zjxu.edu.cn;
lichun.liu@mail.zjxu.edu.cn
with transition metal ions always shows good potential
18
b.CAS Key Laboratory of Standardization and Measurement for Nanotechnology,
CAS Center for Excellence in Nanoscience, National Center for Nanoscience and
Technology, 11 Zhongguancun Beiyitiao, Beijing, 100190, P. R. China E-mail:
zengqd@nanoctr.cn
c. State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing
210093, P. R. China
Electronic Supplementary Information (ESI) available: CCDC numbers: 1471018–
applications,
such as magnetism, catalytic activity and drug
delivery. However, the combination of these ligands and
polyoxometalates haven’t been reported. Thus, in this work, tris[(2–
pyridyl)methyl]amine (TPMA) was selected as the multidentate
flexible ligand to assemble with different metal ions and various
polyoxomolybdates, with the aim for constructing novel organic–
inorganic hybrid materials (Scheme 1). Notably, a series of materials
1471020
crystallographic
DOI: 10.1039/x0xx00000x
(
1
~
3
), 1471022 (4), 1471021(5), 1486195
(
6
), 1486075
(
7
electronic format
), ESI and
see
data in CIF or other
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J. Name., 2016, 00, 1-11 | 1
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consisting of flexible organic amine (TPMA) modified
polyoxomolybdates were obtained:
[Zn2(TPMA)2(H2P2Mo5O23)]·11H2O (1), [Zn2(TPMA)2(Mo8O26)] (2),
[Co2(TPMA)2(Mo8O26)] (3), [Ni2(TPMA)2(Mo8O26)(H2O)2] (4),
[Ni2(TPMA)2(2–PA)(H2O)](PMo12O40) (5), [Cu2(TPMA)2(Mo8O26)] (6),
2[Cu(TPMA)(CrMo6(OH)6O18)]·H[Cu2(TPMA)2(CrMo6(OH)6O18)]·4H2O
(7). All complexes 1–7 shown polyoxomolybdates–based zero–
dimensional (0D) structures, and could be further extended into 3D
Scheme 2 Synthetic route for the TPMA ligand.
supramolecular
frameworks
through
hydrogen
bonding
interactions. In addition, the electrochemical properties of
complexes 1–7 have been investigated. Moreover, some complexes
have efficient photocatalytic activities to degradate Pararosanline
Hydrochloride dye molecule.
Synthesis of compound [Zn2(TPMA)2(H2P2Mo5O23)]·11H2O (1). A
mixture solution of Zn(NO3)2 (29.7 mg, 0.1 mmol), TPMA (29 mg, 0.1
mmol), (NH4)6Mo7O24 (123 mg, 0.1 mmol), H3PO4 (0.5 mL) and H2O
(10 mL) was stirred at room temperature. The pH was adjusted to
5.0 with 4.0 mol·L−1 NaOH, and then the suspension was transferred
to a Teflon–lined reactor and kept under autogenous pressure at
160 °C for 3 days. After slow cooling to room temperature, colorless
needle-like crystals were filtered and washed with distilled water
(yield 47% based on Zn). IR (solid KBr pellet, cm–1): 3500(s), 1687(s),
1513(w), 1498(m), 1024(w), 937(s), 762(w), 733(s).
Synthesis of compound [Zn2(TPMA)2(Mo8O26)] (2). A mixture
solution of Zn(NO3)2 (29.7 mg, 0.1 mmol), TPMA (29 mg, 0.1 mmol),
Na3[CrMo6(OH)6O18]·8H2O (120 mg, 0.1 mmol) and H2O (10 mL) was
stirred at room temperature. The pH was 5.0, and then the
suspension was transferred to a Teflon–lined reactor and kept
under autogenous pressure at 160 °C for 3 days. After slow cooling
to room temperature, colorless needle-like crystals were filtered
and washed with distilled water (yield 31% based on Zn). IR (solid
KBr pellet, cm–1): 3588(s), 1692(s), 1501(m), 1428(s), 1395(s),
1312(m), 960(s), 844(s), 712(s).
Scheme 1 The main ligand (TPMA), auxiliary ligand (2–PA) and extra
auxiliary reagent (Imidazole).
Experimental
Materials and methods
Synthesis of compound [Co2(TPMA)2(Mo8O26)] (3). A mixture
solution of CoCl2 (23.8 mg, 0.1 mmol), TPMA (29 mg, 0.1 mmol),
(NH4)6Mo7O24 (123 mg, 0.1 mmol), imidazole (6 mg, 0.1 mmol) and
H2O (10 mL) was stirred at room temperature. The pH was 5.0, and
then the suspension was transferred to a Teflon–lined reactor and
kept under autogenous pressure at 160 °C for 3 days. After slow
cooling to room temperature, green block crystals were filtered and
washed with distilled water (yield 29% based on Co). IR (solid KBr
pellet, cm–1): 3429(w), 3117(w), 1648(m), 1481(m), 1277(w),
1039(m), 977(s), 841(s), 732(m).
All the chemicals were received as reagent grade and used without
any
further
purification.
The
ligand
TPMA
and
Na3[CrMo6(OH)6O18]·8H2O were synthesized according to
literatures.19 The IR spectra were obtained on a Varian 640 FT/IR
spectrometer with KBr pellet in 400−4000 cm−1 region. Powder X–
ray diffraction (PXRD) was performed on a DX–2600 spectrometer.
The thermal gravimetric analyses (TGA) were carried out in flowing
N2 on a SDT 2960 differential thermal analyzer with a rate of 10
°C/min. Cyclic voltammograms were obtained with a CHI 440A
electrochemical workstation at room temperature. Platinum wire
was used as a counter electrode and Ag/AgCl electrode was used as
a reference electrode. Chemically bulk–modified carbon paste
electrode (CPE) was used as the working electrode. The UV
experiments were carried out on a Thermo EV 201CP.
Synthesis of compound [Ni2(TPMA)2(Mo8O26)(H2O)2] (4).
A
mixture solution of NiCl2 (23.7 mg, 0.1 mmol), TPMA (29 mg, 0.1
mmol), (NH4)6Mo7O24 (123 mg, 0.1 mmol), imidazole (6 mg, 0.1
mmol) and H2O (10 mL) was stirred at room temperature. The pH
was 5.0, and then the suspension was transferred to a Teflon–lined
reactor and kept under autogenous pressure at 160 °C for 3 days.
After slow cooling to room temperature, light yellow block crystals
were filtered and washed with distilled water (yield 26% based on
Ni). IR (solid KBr pellet, cm–1): 3362(m), 3127(m), 1766(s), 1714(m),
1501(m), 1484(s), 1122(s), 1006(s), 926(s), 864(s), 689(m).
Syntheses of TPMA ligand and complexes 1–7
Synthesis of Tris[(2–pyridyl)methyl]amine (TPMA). The synthesis
route of TPMA is shown in the Scheme 2. To a suspension of K2CO3
(7.87 g, 0.057 mol) in 100 mL of MeCN, 2–(chloromethyl) pyridine
hydrochloride (6.28 g, 0.39 mol) was added to produce an orange
suspension. Then, 2–picolylamine (2.09 g, 0.19 mol) was added. The
mixture was stirred vigorously at 80oC for 3 days and the product
was purified by Column Chromatography (1:1 CH2Cl2 / MeOH). The
final product was brown solid powder (5.51 g, 65.7% yield).
Synthesis of compound [Ni2(TPMA)2(2–PA)(H2O)](PMo12O40) (5).
A mixture solution of NiCl2 (23.7 mg, 0.1 mmol), TPMA (29 mg, 0.1
mmol), (NH4)6Mo7O24 (12.3 mg, 0.1 mmol), 2–picolinic acid (15.2
mg, 0.1 mmol), H3PO4 (0.5 mL) and H2O (10 mL) was stirred at room
2 | J. Name., 2016, 00, 1-11
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temperature. The pH was adjusted to 5.0 with 4 mol·L−1 NaOH, and Cambridge Crystallographic Data Center, their crystal structures can
then the suspension was transferred to a Teflon–lined reactor and be obtained with CCDC reference numbers 1471018–1471020
kept under autogenous pressure at 160 °C for 3 days. After slow (1~3), 1471022 (4), 1471021(5), 1486195 (6), 1486075 (7),
cooling to room temperature, black columnar crystals were filtered respectively.
and washed with distilled water (yield 15% based on Ni).
Synthesis of Complex [Cu2(TPMA)2(Mo8O26)] (6). A mixture Results and discussion
solution of Cu(NO3)2 (24.3 mg, 0.1 mmol), TPMA (29.2 mg, 0.1
Structural description of Complexes 1–7.
mmol), (NH4)6Mo7O24 (123 mg, 0.1 mmol), imidazole (6 mg, 0.1
mmol) and H2O (10 mL) was stirred at room temperature. The pH
[Zn2(TPMA)2(H2P2Mo5O23)]·11H2O (1). Compound 1 crystallizes in
was adjusted to 2.5 with 4.0 mol·L−1 HCl, and then the suspension
the monoclinic space group P21/c, and consists of one
4–
]
was transferred to
a Teflon–lined reactor and kept under
[H2P2Mo5O23
(abbreviated as P2Mo5) polyoxoanion, two TPMA
autogenous pressure at 160 °C for 3 days. After slow cooling to
room temperature, green block crystals were filtered, washed with
distilled water and separated manually (yield 11% based on Cu). IR
(solid KBr pellet,cm–1): 3455(w), 3131(w), 2933(w), 1611(s), 1432(s),
1369(w), 1312(w), 1273(w), 935(s), 824(s), 689(w).
ligands, two Zn(II) ions and eleven interstitial water molecules.
22
Bond valence sum calculations show that all molybdenum atoms
are in the +6 oxidation state, and zinc atoms are in the +2 oxidation
state. Due to the principle of charge conservation, two protons are
added in the P2Mo5 polyoxoanion.
In the structure of 1, there are two crystallographically
independent Zn(II) ions (Fig. 1a). Zn1 ion is five–coordinated in a
triangular bipyramid configuration by one O atom from P2Mo5
polyoxoanion (Mo–O) and four N atoms from TPMA ligand, in which
three N atoms from pyridine generate an approximate triangle
plane, and O atom and the fourth N atom serve as vertices. Zn2 ion
Synthesis
of
Complex
2[Cu(TPMA)(CrMo6(OH)6O18)]·H[Cu2(TPMA)2(CrMo6(OH)6O18)]·4H2
O (7). A mixture solution of Cu(NO3)2 (24.3 mg, 0.1 mmol), TPMA
(29.2 mg, 0.1 mmol), Na3[CrMo6(OH)6O18]·8H2O (120 mg, 0.1 mmol)
and H2O (10 mL) was stirred at room temperature. The pH was 5.0,
and then the suspension was transferred to a Teflon–lined reactor
and kept under autogenous pressure at 160 °C for 3 days. After
slow cooling to room temperature, light yellow block crystals were
filtered and washed with distilled water (yield 23% based on Cu). IR
(solid KBr pellet, cm–1): 3469(w), 3058(w), 1590(s), 1426(s),
1306(m), 1151(m), 1011(s), 944(s), 780(s), 572(w).
is also five–coordinated in
a distorted triangular bipyramid
geometry by four N atoms from another TPMA ligand and one O
atom from the same P2Mo5 polyoxoanion (P–O). The bond lengths
ranges of Zn–O and Zn–N are 1.917(6)–1.977(5) Å and 2.066(8)–
2.245(7) Å, respectively (Table S1). The unit of compound 1 are
connected by intermolecular hydrogen bonds [C(26)–H(26)…O(16),
3.234(11) Å] into a 1D supramolecular left–handed chain, and the
adjacent chains are right–handed chains, therefore compound 1 is
achiral complex (Fig. 1b and Fig. 1c). Then adjacent 1D chains are
further linked into 2D supramolecular layer through hydrogen
bonds [C(36)–H(36)…O(22), 3.205 (12) Å] (Fig. 1d). 2D layers are
extended into a 3D supramolecular framework through H–bonding
interaction [C(30)–H(30)…O(15), 3.363 (12) Å] (Fig. 1e).
Preparation of complexes 1–7 bulk–modified CPEs: The
preparation method:20 The bulk–modified Carbon Paste Electrode
(CPE) was fabricated by mixing 100 mg graphite powder and 10 mg
target compound in an agate mortar for approximately 30 min to
achieve a uniform mixture; then two drops methylsilicone oil was
added and stirred with a copper rod. The homogenized mixture was
packed into a 2 mm inner diameter glass tube and the tube surface
was wrapped with weighing paper. The electrical contact was
established with the copper wire through the back of the electrode.
The bare CPE was prepared by similar process without target
complexes.
Zn2(TPMA)2(Mo8O26)(2),
Co2(TPMA)2(Mo8O26)(3)
and
Cu2(TPMA)2(Mo8O26)(6). Complex 2 crystallizes in the orthorhombic
4–
]
space group Pbca, and consists of one [Mo8O26
(abbreviated as
Mo8) polyoxoanion, two TPMA ligands and two Zn(II) ions. Bond
valence sum calculations 22 show that all molybdenum atoms are in
the +6 oxidation state, and zinc atoms are in the +2 oxidation state.
In compound 2, the coordination environments of the two Zn(II)
ions are similar to each other (Fig. 2a). Zn ion is five–coordinated in
a triangular bipyramid geometry by four N atoms from TPMA ligand
and one O atom from Mo8 polyoxoanion (Mo–O). The bond lengths
ranges of Zn–O and Zn–N are 1.998(2) Å and 2.046(3)–2.219(3) Å,
respectively (Table S1). Interestingly, it is worth mentioning that the
Mo8 structure is transformed from the starting material CrMo6 and
this kind of transformation between different POM structures have
been reported in the literatures.23
X-ray crystallography. Single crystal X–ray diffraction analysis data
for complexes 1–7 were collected with an Oxford Diffraction Gemini
R Ultra diffract–ometer with graphite–monochromated Mo–Kα (λ =
0.71073 Å) or Cu–Kα (λ = 1.54184 Å) at 296 K. All structures were
solved by direct methods and refined on F2 by full–matrix least–
squares methods using the SHELXTL package. 21 In the structure of
compound 1, hydrogen atoms attached to water molecules with
partial site occupancy were not located. A summary of the crystal
data and structure refinements of complexes 1–7 are provided in
Table 1. Selected bond lengths and angles are listed in Table S1.
Crystallographic data for complexes 1–7 have been deposited in the
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Table 1 Crystal data and structure refinements for complexes 1–7.
Complexes
1
C36H60Mo5N8O34P2Zn2
1821.30
296(2)
2
C36H36Mo8N8O26Zn2
1894.99
296(2)
3
C36H36Mo8N8O26Co2
1882.11
296(2)
4
C36H40Mo8N8O28Ni2
1917.67
296(2)
Empirical formula
Formula weight
Temperature/K
Crystal system
monoclinic
P21/c
orthorhombic
Pbca
orthorhombic
Pbca
monoclinic
P21/n
Space group
a/Å
11.8566(5)
19.7359(8)
26.2178(10)
90
16.6740(4)
15.9270(3)
19.1977(4)
90
16.7082(3)
15.9095(3)
19.2987(3)
90
12.2553(4)
15.3666(4)
15.4604(5)
90
b/Å
c/Å
α/°
β/°
γ/°
100.164(4)
90
90
90
110.489(4)
90
90
90
Volume/Å3
6038.7(4)
4
5098.28(19)
4
5129.96(17)
4
2727.36(14)
2
Z
ρcalcg/cm3
2.003
2.469
2.437
2.3349
μ/mm–1
1.938
2.915
2.609
2.540
F(000)
3616
3648
3624
1830.6
Radiation
MoKα
MoKα
MoKα
MoKα
Reflections collected
Independent reflections
Rint
24542
12810
15244
12597
10612
4498
5988
4794
0.0465
0.0226
0.0215
0.0273
GOOF
1.127
1.055
1.057
1.056
R1,wR2 [I>=2σ (I)]
R1,wR2 [all data]
0.0731, 0.1708
0.0942, 0.1789
0.0214, 0.0472
0.0291, 0.0495
0.0237, 0.0508
0.0340, 0.0547
0.0292, 0.0634
0.0394, 0.0692
aR1 = Σ||Fo|–|Fc||/Σ|Fo|, bwR2 = Σ[w(Fo2–Fc2)2]/Σ[w(Fo2)2]1/2
.
Complexes
Empirical formula
Formula weight
Temperature/K
Crystal system
Space group
a/Å
5
C42H42Mo12N9O43PNi2
2660.48
296(2)
6
7
C72H99Mo18N16O76Cr3Cu4
4541.75
C36H36Mo8N8O26Cu2
1891.33
296(2)
296(2)
monoclinic
P21/c
orthorhombic
Pbca
triclinic
ꢀ
P1
11.2559(4)
24.1685(11)
25.7463(9)
90
16.8760(3)
15.9080(3)
18.9788(3)
90
14.4947(6)
15.7549(4)
15.8183(6)
99.314(3)
116.519(4)
91.546(3)
3169.4(2)
1
b/Å
c/Å
α/°
β/°
100.287(4)
90
90
γ/°
90
Volume/Å3
6891.4(5)
4
5095.10(15)
4
Z
ρcalcg/cm3
μ/mm–1
2.564
2.466
2.380
18.982
2.81
2.718
F(000)
5104
3640
2195
Radiation
Reflections collected
Independent reflections
Rint
CuKα
MoKα
MoKα
29399
15971
23137
13356
5920
11152
0.0561
0.0276
0.0227
GOOF
1.059
1.051
1.021
R1, wR2 [I>=2σ (I)]
R1, wR2 [all data]
0.0525, 0.1122
0.0260, 0.0521
0.0386, 0.0582
0.0280, 0.0610
0.0392, 0.0651
0.0935, 0.1315
aR1 = Σ||Fo|–|Fc||/Σ|Fo|, bwR2 = Σ[w(Fo2–Fc2)2]/Σ[w(Fo2)2]1/2
.
4 | J. Name., 2016, 00, 1-11
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Fig. 1 The structure of compound 1: (a) Coordination environments for Zn ions and P2Mo5 polyoxoanion (The hydrogen atoms are omitted
for clarity). (b) and (c) The ball–and–stick and space–filling view of left–handed 1D chain by hydrogen bonding interactions along black
arrow direction, respectively. (d) 2D supramolecular layer and (e) 3D supramolecular framework formed by hydrogen bonding interactions.
TPMA are coordinated with Zn(II) ions and then located on both molecule. The bond lengths ranges of Cu–O and Cu–N are 1.943(4)–
sides of Mo8 to form a sandwich structure. The sandwich structures 2.782(5) Å and 1.945(5)–1.993(5) Å, respectively (Table S1). TPMA
are connected by intermolecular hydrogen bonds [C(16)– are coordinated with Ni(II) ions and then located on both sides of
H(16)…O(3), 3.182(4) Å] into a 2D supramolecular layer (Fig. 2b). 2D Mo8 to form a sandwich structure. The sandwich structures are
layers are extended into a 3D supramolecular framework through connected by intermolecular hydrogen bonds [C(16)–H(16)…O(13),
H–bonding interaction [C(6)–H(6B)…O(8), 3.359 (4) Å] (Fig. 2c).
3.102(4) Å] into a 2D supramolecular layer (Fig. 3b). 2D layers are
Complexes 2, 3 and 6 are isostructural and possess different extended into a 3D supramolecular framework through H–bonding
metal ions. In compound 3, the bond lengths ranges of Co–O and interaction [C(2)–H(2)…O(12), 3.171 (4) Å] (Fig. 3c).
Co–N are 1.9695(19) Å and 2.045(2) Å–2.208(2) Å, respectively
[Ni2(TPMA)2(2–PA)(H2O)](PMo12O40) (5) Complex 5 crystallizes in
(Table S1). In compound 6, the bond lengths ranges of Cu–O and
3–
the monoclinic space group P21/c, and consists of one [PMo12O40]
Cu–N are 1.930(2) Å and 2.037(3) Å –2.089(3) Å, respectively (Table
S1).
(abbreviated as PMo12) polyoxoanion, two TPMA ligands, one 2–PA
ligand, two Ni(II) ions and one coordinated water molecule. Bond
[Ni2(TPMA)2(Mo8O26)(H2O)2] (4) Compound 4 crystallizes in the valence sum calculations 22 show that all molybdenum atoms are in
4–
monoclinic space group
P
21/n
, and consists of one [Mo8O26
]
the +6 oxidation state, and nickel atoms are in the +2 oxidation
(abbreviated as Mo8) polyoxoanion, two TPMA ligands, two Ni(II) state.
ions and two coordinated water molecules. Bond valence sum
In complex 5, the coordination environments of the two Ni(II)
22
calculations
show that all molybdenum atoms are in the +6 ions are different (Fig. 4a). Ni1 ion is six–coordinated in a distorted
oxidation state, and nickel atoms are in the + 2 oxidation state.
octahedral geometry by four N atoms from TPMA ligand, one N
In compound 4, the coordination environments of the two Ni(II) atom and one O(O–H) atom from 2–PA. Ni2 ion is six–coordinated
ions are same (Fig. 3a). Ni ion is six–coordinated in a distorted in a distorted octahedral geometry by four N atoms from another
octahedral geometry by four N atoms from TPMA ligand, one O TPMA ligand, one O(C=O) atoms from the same 2–PA and one O
atom from Mo8 polyoxoanion (Mo–O) and one O atom from water atom from water molecule. The bond lengths ranges of Ni–O and
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Fig. 3 The structure of complex 4. (a) Coordination environments for
Ni ions and Mo8 polyoxoanion (The hydrogen atoms are omitted for
clarity). (b) 2D supramolecular layer by H bonds interactions. (c) 3D
supramolecular framework by H bonds interactions.
Fig. 2 The structure of compound 2. (a) Coordination environments
for Zn ions and Mo8 polyoxoanion (The hydrogen atoms are omitted
for clarity). (b) 2D supramolecular layer by H bonds interactions. (c)
3D supramolecular framework by hydrogen bonding interactions.
valence sum calculations 22 show that all molybdenum atoms are in
the +6 oxidation state, chrome atoms are in the +3 oxidation state,
and copper atoms are in the +2 oxidation state.
Ni–N are 2.002(7)–2.100(7) Å and 2.046(8)–2.112(9) Å, respectively
(Table S1).
Two Ni(II) ions are bridged by the carboxyl of 2–PA to produce a
In the first structure of compound 7, Cu1 ion is five–coordinated
in a trigonal bipyramid geometry by four N atoms from TPMA ligand
and one O atom from CrMo6 polyoxoanion. In the second structure
of 7, the coordination environments of the two Cu ions are same
and symmetry related (Fig. 5a), Cu2 ion is also five–coordinated in a
trigonal bipyramid geometry by four N atoms from TPMA ligand and
one O atom from CrMo6 polyoxoanion. The bond lengths ranges of
Cu–O and Cu–N are 1.914(4) Å–1.994(4) Å and 2.018(6) Å–2.079(7)
Å, respectively (Table S1).
dinuclear Ni(II) cluster. The dinuclear Ni(II) cluster are connected by
intermolecular hydrogen bonds [C(39)–H(39)…O(39), 3.145(11) Å;
C(15)–H(15)…O(31), 3.128(11) Å] into a 1D supramolecular ‘Z’–type
chain (Fig. 4b), and the adjacent chains are extended into a 3D
supramolecular framework through H–bonding interaction [C(7)–
H(7)…O(18), 3.127 (12) Å; C(8)–H(8)…O(5), 3.125 (12) Å] (Fig. 4c).
The two independent structures are linked by intermolecular
2[Cu(TPMA)(CrMo6(OH)6O18)]·H[Cu2(TPMA)2(CrMo6(OH)6O18)]·4H2
hydrogen bonds [C(21)–H(21)…O(21), 3.024(11) Å] into
a 1D
ꢀ
P1.
O (7). Compound 7 crystallizes in the triclinic space group
supramolecular chain with the connection mode of ABAB (Fig. 5b),
and the adjacent chains are connected by intermolecular hydrogen
bonds [C(3)–H(3)…O(23), 3.074(11) Å] into a 2D supramolecular
Intriguingly, there are two kinds of independent structures and two
interstitial water molecules in 7. The first structure consists of one
3-
]
[CrMo6(OH)6O18
(abbreviated as CrMo6) polyoxoanion, one TPMA
layer (Fig. 5c). Further, 2D layers are extended into
a 3D
ligands and one copper ion. The second structure consists of one
CrMo6 polyoxoanion, two TPMA ligands and two copper ions. Bond
supramolecular framework through H–bonding interaction [C(20)–
H(20)…O(7), 3.156 (12) Å] (Fig. 5d).
6 | J. Name., 2016, 00, 1-11
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Fig. 4 The structure of compound 5. (a) Coordination environments for Ni ions (The hydrogen atoms are omitted for clarity). (b) ‘Z’–type 1D
chain by H bonds interactions. (c) 3D supramolecular framework by H bonds interactions.
Fig. 5 The structure of compound 7. (a) Coordination environments for Cu ions (The hydrogen atoms are omitted for clarity). (b) The 1D
chain by H bonds interactions in the connection mode of ABAB. (c) 2D supramolecular layer and (d) 3D supramolecular framework
connected by H bonds interactions.
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(a)
(b)
(c)
(d)
(e)
(f)
Fig. 6 Cyclic voltammograms of 1–6 CPEs in 0.5 M Na2SO4 + 0.1 M H2SO4 aqueous solution at distinct scanning rates (from inside to out: 50,
100, 150, 200, 250, 300, 350, 400, 450, 500 mV s −1) respectively.
FT–IR Spectra and Powder X–ray Diffraction. The IR spectra of to the characteristic peaks of νas (Mo−Ot) and νas (Mo−O−Mo). For
complexes 1–7 are shown in Fig. S1. For compound 1, the bands at compound 5, the bands at 936, 803, 728, 1090 cm–1 could be
856, 793, 627 and 963 cm–1 could be ascribed to the characteristic ascribed to the characteristic peaks of νas (Mo−Ot), νas (Mo−O−Mo)
peaks of νas (Mo−Ot), νas (Mo−O−Mo) and νas (P−O). For compound 2, and νas (P−O), the bands at 1619 cm–1 could be ascribed to the
the bands at 1125, 826 and 750 cm–1 could be ascribed to the characteristic peaks of νas (C=O) from the ancillary ligand of 2–PA.
characteristic peaks of νas (Mo−Ot) and νas (Mo−O−Mo). For For compound 6, the bands at 963, 832 and 709 cm–1 could be
compound 3, the bands at 985, 779 and 742cm–1 could be ascribed ascribed to the characteristic peaks of νas (Mo−Ot) and νas
to the characteristic peaks of νas (Mo−Ot) and νas (Mo−O−Mo). For (Mo−O−Mo). For compound 7, the bands at 1016, 954 and 793cm–1
compound 4, the bands at 994, 829 and 728 cm–1 could be ascribed could be ascribed to the characteristic peaks of νas (Mo−Ot) and νas
8 | J. Name., 2016, 00, 1-11
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(Mo−O−Mo). For 1–7, the bands in the region of 1700 to 1200 cm–1
As for 1−7, the redox peaks may arise from the redox process of
could be ascribed to the characteristic peaks of the TPMA ligand. Mo-based polyoxoanion clusters, but the pairs number of redox
The bands in the region of 3750 to 3000 cm–1 could be ascribed to peaks are different which may be caused by the diverse
the characteristic peaks of the νas (−OH) from the water molecules.
coordination modes of those complexes.25 The cathodal peak
To indicate the phase purities of complexes 1–7, PXRD potentials of complexes 1−7 move to the minus orientation, and the
experiments were carried out. As shown in Fig. S2, diffraction peaks corresponding anodal peak potentials move toward the plus
of both simulated and experimental patterns match well in the key orientation with increasing scanning rates.
positions, which indicate the phase purity of bulky samples. The
Photocatalytic Activities. It is well known that a wide range of
polyoxomolybdates possess photocatalytic activities in the
degradations of organic dyes under UV irradiation.26 Thus, we
explored the photocatalytic performances of complexes 1–7 for the
photodegradation of Pararosanline Hydrochloride with UV
irradiation through a typical process: Complexes 1–7 (20 mg) were
added to the 50 mL aqueous solution of Pararosanline
Hydrochloride (6 mg/L), respectively, and stirred for about 15
minutes to ensure the equilibrium of the resulting solution. Then
the solution was exposed to UV irradiation from a 100 W Hg lamp (λ
= 365 nm). The solution was kept for stirring during the irradiation.
At every 30 min intervals, 5 mL of sample was taken out for UV
analysis.
differences in intensity may be aroused from the preferred
orientation of the powder samples. 24
Thermal Stability Analyse. As shown in Fig. S3, the thermal
stabilities of complexes 1–8 were investigated under N2 atmosphere
from room temperature to 800 oC. For 1, two steps of weight loss
are observed. The first weight loss of 2.77 % (calc. 10.87 %) occurs
before 296 oC, which is attributed to the loss of eleven free water
molecules. The second weight loss is ascribed to the decomposition
of the remaining structure. As for 2, its structure starts to collapse
when the temperature reaches to 363 oC. Similarly, the collapsing
temperature for 3 is 358 oC. For 4, there are two steps of weight
loss. The first weight loss of 2.00 % (calc. 1.88 %) occurs before 247
oC, which is ascribed to the loss of two coordinated water
molecules. The second weight loss is attributed to the
decomposition of the remaining structure. For 5, its structure starts
to collapse when the temperature reaches to 134 oC. For 6, its
structure starts to collapse when the temperature reaches to 307oC
without the process of the loss of water molecules. For 7, two steps
of weight loss are observed. The first weight loss of 0.38 % (calc.
0.58 %) occurs before 294 oC, which is attributed to the loss of two
free water molecules. The second weight loss is ascribed to the
decomposition of the remaining structure. According to the results
of the above analysis, the basic skeletons of all the complexes
display good thermal stability.
As observed in Fig. 7, complexes 1, 4, 5, 6 and 7 display excellent
degradation effect for Pararosanline Hydrochloride. It is obvious
that the absorption peaks of Pararosanline Hydrochloride
decreased significantly with illumination time. The calculation
results show that the conversion of Pararosanline Hydrochloride
after irradiation in 3 hours is 93.25% for 1, 87.87% for 4, 76.48% for
5, 81.31% for 6, 90.16% for 7, respectively. Though complexes 2 and
3 have similar structures with complex 6, but their photocatalytic
activities are far less than that of complex 6. As shown in Fig. S5 and
Fig. 7f, their degradation efficiency for Pararosanline Hydrochloride
are only 31.71% and 32.17%, respectively, this result maybe caused
by the difference of their center metal ions. By contrast, the order
of photocatalytic activity is 1 ﹥ 7 ﹥ 4 ﹥ 6 ﹥ 5 (Fig. 7f). The
photocatalytic behaviors of those five complexes indicate that they
may be good photocatalysts for the photodegradation of organic
dyes.
Electrochemical Properties. The electrochemical properties of 1–7
have been investigated in detail in 0.5 M Na2SO4 + 0.1 M H2SO4
aqueous solution (Fig. 6 and Fig. S4). In the potential range from 0–
500 mV, there are two pairs of reversible redox peaks (I–I' and II–II')
for compound 1. The mean peak potentials E1/2 = (Ecp + Eap) / 2 (scan
rates: 200 mV/s) are 273 and 83 mV, respectively. In the potential
range from 0–500 mV, there are three pairs of reversible redox
peaks (I–I', II–II', III–III') for compound 2. The mean peak potentials
E1/2 = (Ecp + Eap) / 2 (scan rates: 200 mV/s) are 394, 248 and 101 mV,
respectively. While compound 3 shows two pairs of weak redox
peaks. For compound 4, there are three pairs of reversible redox
peaks (I–I', II–II', III–III') in which the mean peak potentials E1/2 = (Ecp
+ Eap) / 2 (scan rates: 200 mV/s) are 372, 239 and 112 mV,
respectively. In the potential range from -200–500 mV, there are
three pairs of obvious reversible redox peaks (I–I', II–II', III–III') for
compound 5. The mean peak potentials E1/2 = (Ecp + Eap) / 2 (scan
rates: 200 mV/s) are 344, 125 and –168 mV, respectively. In the
potential range from 0–400 mV, there are two pairs of reversible
redox peaks (I–I' and II–II') for 6, and their mean peak potentials E1/2
= (Ecp + Eap) / 2 (scan rates: 200 mV/s) are 222 and 110 mV,
respectively. In the potential range from 100–600 mV, there is only
one pair of weak redox peak (I–I') for complex 7. The mean peak
potentials E1/2 = (Ecp + Eap) / 2 (scan rates: 200 mV/s) is 221 mV.
Conclusions
In this contribution, a series of organic–inorganic hybrid complexes
based on different types of polyoxomolybdates and transition
complexes have been successfully synthesized under hydrothermal
conditions. Complexes 1–7 show polyoxomolybdates–based zero–
dimensional (0D) structures, and can be further extended into
three–dimensional (3D) supramolecular frameworks through
hydrogen bonding interactions. Intriguingly, four kinds of
polyoxometalates (P2Mo5, Mo8, PMo12, CrMo6) present in
complexes 1–7 and this indicates the diversity of
polyoxomolybdates. Additionally, the electrochemical properties of
complexes 1–7 have been investigated. Moreover, some complexes
have efficient photocatalytic activities to degradate Pararosanline
Hydrochloride dye molecule. It is believed that this work could
provide useful information for the construction of multifunctional
polyoxomolybdates–based organic–inorganic hybrid materials and
various architectures of those materials could be observed
consistently.
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(a)
(b)
(c)
(d)
(e)
(f)
Fig. 7 Photocatalytic activities of complexes 1 (a), 4 (b), 5 (c), 6 (d), 7 (e) and the comparison for their degradation rates of complexes 1-7 (f),
inside photo: before (left) and after (right) illumination.
Acknowledgements
Notes and references
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Financial support from the National Natural Science Foundation of
China (21371078, 21401077, 21472029), the National Key Basic
Research Program of China (2013CB934200) is gratefully
acknowledged.
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DOI: 10.1039/C6RA21603J
Table of Contents Entry
A Series of Organic–inorganic Hybrid Materials Consisting of Flexible Organic
Amine Modified Polyoxomolybdates: Synthesis, Structures and Properties
A series of hybrid materials consisting of tris[(2–pyridyl)methyl]amine modified
polyoxomolybdates were obtained and some complexes have efficient photocatalytic
activities to degradate Pararosanline Hydrochloride dye molecule.