Assembly of an undeca-nuclear nickel substituted POM through polycarboxylate ligand

Article abstract of DOI:10.1039/c2dt12507b

An undeca-nuclear nickel substituted POM, namely [Ni(H₂O) ₆][Ni₁₁(PW₉O₃₄)₂(IDA) ₃(en)₂(Hen)₂(OH)₆]·(H ₂O)₇·(H₂en)₂ (1) (en = 1,2-ethylenediamine, H₂IDA = iminodiacetic acid), was synthesized through hydrothermal reaction of Na₆PW₉O₃₄, en, H₂IDA and NiCl₂·6H₂O. Single-crystal structure reveals that 1 can be viewed as Ni₆PW₉ and Ni₅PW₉ units linked by a μ₃-O bridge and two IDA^2- ligands. Magnetic investigation indicates the presence of dominantly ferrimagnetic interactions within the Ni₁₁ core. Electrochemistry study shows that 1 displays a stable and reproducible voltammetric graph.

Full text of DOI:10.1039/c2dt12507b

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A dodecanuclear Zn cluster sandwiched by polyoxometalate ligands
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COMMUNICATION
Assembly of an undeca-nuclear nickel substituted POM through
polycarboxylate ligand†
Yun-Yun Zheng, Ru Wen, Xiang-Jian Kong, La-Sheng Long,* Rong-Bin Huang and Lan-Sun Zheng
Received 30th December 2011, Accepted 25th April 2012
DOI: 10.1039/c2dt12507b
transition-metal substituted POMs, since they are negatively
charged ligands. Accordingly, we, in this work, use iminodiace-
tic acid or 1-piperidine acid, NiCl2·6H2O, 1,2-ethylenediamine,
and Na9[A-α-PW9O34]·nH2O (namely PW9) to synthesize metal
cluster substituted POMs and report herein crystal structures,
magnetic and electrochemical properties of three nickel substi-
tuted POMs, namely [Ni(H2O)6][Ni11(PW9O34)2(IDA)3(en)2-
(Hen)2(OH)6]-·(H2O)7·(H2en)2 (1) (H2IDA = iminodiacetic acid,
en = 1,2-ethylenediamine).
An undeca-nuclear nickel substituted POM, namely [Ni-
(H2O)6][Ni11(PW9O34)2(IDA)3(en)2(Hen)2(OH)6]·(H2O)7·(H2en)2
(1) (en = 1,2-ethylenediamine, H2IDA = iminodiacetic acid),
was synthesized through hydrothermal reaction of Na6-
PW9O34, en, H2IDA and NiCl2·6H2O. Single-crystal struc-
ture reveals that 1 can be viewed as Ni6PW9 and Ni5PW9
units linked by a μ3-O bridge and two IDA2− ligands.
Magnetic investigation indicates the presence of dominantly
ferrimagnetic interactions within the Ni11 core. Electrochem-
istry study shows that 1 displays a stable and reproducible
voltammetric graph.
Experimental section
Materials and general methods
All solvents and starting materials for the synthesis were pur-
chased commercially and were used as received. Infrared spectra
were obtained in KBr discs on a Nicolet AVATAR FT-IR360
spectrometer in the range of 4000–400 cm−1 region. Elemental
analyses of C, H and N were performed on a elementar Vario
ELIII Elemental Analyzer. Elemental analyses of P, W and
Ni were determined with a GP3.5 -D1 ICP-AES. Thermogravi-
metric analyses (TGA) were carried out in a oxygen stream
using SDT-Q600 TG/DTA equipment with a heating rate of
10 °C min−1. Powder X-ray diffraction (PXRD) data were
recorded on a X’pert PRO X-ray powder diffractometer (CuKα,
λ = 0.1504 nm) at room temperature. Electronic absorption
spectra were recorded on a CHI 631B electrochemical work-
station at room temperature under a nitrogen atmosphere.
Na9[A-α-PW9O34]·nH2O (PW9) were prepared by a literature
method (Inorganic Syntheses, John Wiley & Sons, New York,
1990, vol. 27, p. 85). The syntheses of compounds 1 to 3 are
shown in Scheme 1.
Introduction
Polynuclear 3d transition-metal clusters have attracted consider-
able interest, due to their unique structures and potential
applications in catalysis, magnetism and electrochemistry.1
Polyoxometalates (POMs), featuring enriched oxygen atoms on
their surface, are regarded as excellent inorganic multidentate
O-donor ligands to construct polynuclear 3d transition-metal
substituted POMs.2 Compared with organic ligands, POMs
possess their own structural features in size, shape and symmetry,
which often lead to their playing different structure-directing
roles in the formation of polynuclear metal clusters.
Although a lot of polynuclear 3d transition-metal substituted
POMs with unique structures and interesting properties have
been synthesized,3–8 most of them are constructed either through
POMs or POMs and neutral organic ligands, those constructed
from both POMs and polycarboxylate remain rare.9,10
Amino acids, such as, glycine and iminodiacetic acid
(H2IDA), have been proved to be excellent ligands in the con-
struction of metal clusters.11,12 More significantly, introducing
these ligands into the transition-metal substituted POMs
would favor increasing the number of metal ions in the 3d
Synthesis of [Ni(H2O)6][Ni11(PW9O34)2(IDA)3(en)2(Hen)2
(OH)6]·(H2O)7·(H2en)2 (1). PW9 (0.30 g, 0.11 mmol),
State Key Laboratory of Physical Chemistry of Solid Surface and
Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China.
E-mail: lslong@xmu.edu.cn; Fax: +86 592 218 3047
†Electronic supplementary information (ESI) available: X-ray crystallo-
graphic files in cif format, the stacking picture, selected bond distances
and the XRD in figure format for 1, 2 and 3. CCDC reference numbers
861305–861307. For ESI and crystallographic data in CIF or other elec-
tronic format see DOI: 10.1039/c2dt12507b
Scheme 1 The simple synthetic chart for 1 to 3.
Dalton Trans., 2012, 41, 9871–9875 | 9871
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NiCl2·6H2O (0.80 g, 3.5 mmol), H2IDA (0.266 g, 2.0 mmol)
and en (0.3 mL) were mixed in 10.0 mL 0.5 M NaAc with stir-
ring at room temperature. After stirring for about 30 min, the
solution was transferred and sealed in a 25 mLTeflon-lined stain-
less steel container. The container was heated to 170 °C and held
at that temperature for 5 days, then cooled to 100 °C at a rate of
4 °C h−1. After 17 h, the solution was cooled to room tempera-
ture with a rate of 4 °C h−1. Green plate crystals 1 (142.3 mg)
were collected by filtration in 39.7% yield (based on Na9PW9-
O34). Anal. Calcd (Found) for 1: Ni, 11.25 (11.09); W, 52.85
(52.82); P, 0.99 (0.91); C, 4.60 (4.75); H, 1.66 (1.87); N: 3.36
(3.49). IR Spectra for 1 (KBr, cm−1): 3432s, 2950w, 1635s,
1586m, 1544m, 1460w, 1388w,1034s, 941s, 849s, 798s, 719m,
510m.
in an equilateral triangle with three on the vertex of the triangle
and the remaining in the middle of the edge. However, there are
differences between 1 and Yang’s compounds. In 1, each Ni2+
ion on the vertex is chelated with an IDA2− ligand, while two
Ni2+ ions in the middle of the edges are respectively coordinated
to a Hen+ ion, and the third Ni2+ on the middle of the edge is
coordinated with a μ3-O bridge linked to the Ni5PW9 unit. In
contrast, the Ni5PW9 unit has not been reported yet. The five
Ni2+ ions in the Ni5PW9 unit are arranged in an isosceles trape-
zoid with four Ni2+ ions on the vertex of the isosceles trapezoid
and one Ni2+ ion in the middle of the longer edge in the iso-
sceles trapezoid. Each Ni2+ ion in the shorter edge of the iso-
sceles trapezoid, locating in octahedron geometry, is coordinated
by one mondentate carboxylate oxygen atom from IDA2−
ligand, two μ2-O from PW9, two μ3-O from the PW9 and one
water molecule respectively. Of the three Ni2+ in the longer
edge, two on the vertex are coordinated by two nitrogen atoms
from one en, one oxygen atom from IDA2− ligand, two μ2-O
and one μ3-O from the PW9, one in the middle of the longer
edge in the isosceles trapezoid is coordinated by one terminal
H2O, two μ2-O and three μ3-O respectively from the PW9. It was
mentioned that 1 is the third example of nickel substituted POMs
with the number of the nickel ions higher than 10 reported so
Synthesis of [Ni6PW9O34(HPA)2(OH)3(en)3(H2O)2]·(H2O)13 (2).
Compound 2 was prepared in the same way as for 1, except that
the H2IDA (2.0 mmol) was replaced with HPA (2.0 mmol).
Green plate crystals 2 (104.5 mg) were collected by filtration in
28.0% yield (based on Na9PW9O34). Anal. Calcd (Found) for 2:
Ni, 10.54 (10.53); W, 49.51 (51.23); P, 0.93 (0.91); C, 6.47
(6.51); H, 2.38 (2.19); N, 3.35 (3.39). IR Spectra for 2
(KBr, cm−1): 3437s, 2950w, 1644s, 1452w, 1378w, 879m, 783s,
713s, 604m, 489m.
far, the other two are [Ni(enMe)2]3[H6Ni20P4W34(OH)4O136
-
(enMe)8(H2O)6]·12H2O7a and [Ni12(OH)9WO4(W7O26(OH))-
(PW9O34)3]25− 7c respectively. The bond lengths in 1 are 1.66
(2)–2.515(14) Å for W–O and 1.46 (2)–1.58(2) Å for P–O, com-
parable to those of 1.692–2.526 Å for W–O and 1.528–1.558 Å
for P–O in nickel substituted POMs Ni207a and Ni12.7c The bond
lengths of Ni–O, Ni–N in 1 are 1.96(2)–2.25(3) and 2.027(16)–
2.23(3) Å respectively, slightly longer than those in nickel sub-
Synthesis of [Ni6PW9O34(H2IDA)2(HIDA)(OH)3(Hen)3]·Cl2·
(H2O)11 (3). Compound 3 was prepared in the same way as for
1, except that 2.5 mmol H2IDA was used in the reaction. Green
tetrahedral crystals 3 (98.1 mg) were collected by filtration in
25.0% yield (based on Na9PW9O34). Anal. Calcd (Found) for 3:
Ni, 10.21 (10.23); W, 48.53 (48.93); P, 0.90 (0.94); C, 6.21
(6.30); H, 2.03 (1.82); N, 3.62 (3.65). IR Spectra for 3 (KBr,
cm−1): 3437s, 2948w, 1618s, 1456w, 1388w, 1041s, 950s,
868m, 780s, 708s, 500m.
7a
stituted POMs Ni20 and Ni12,7c but comparable to those in
the organic ligand-based Ni-clusters of Ni11 and Ni14.14b The
14a
separations of Ni⋯Ni are 2.992 to 3.614 Å, longer than those in
Ni6PW9 reported previously.7b
Crystallography. Data collections were performed on
a
In order to confirm that it is the IDA2− ligand that plays a key
contribution in the formation of 1, HPA ligand was used to syn-
thesize transition-metal substituted POMs under similar synthetic
conditions as described for 1. In this case, compound 2 [Ni6-
PW9O34(HPA)2(OH)3(en)3(H2O)2]·(H2O)13 was obtained. Single-
crystal structural analysis reveals that 2 crystallizes in the space
group Pna21. As shown in Fig. 2a, the six Ni2+ ions were
arranged in an equilateral triangle with three Ni2+ ions on the
vertex of the triangle and the remaining in the middle of the
edge of the equilateral triangle, similar to that reported by Yang
and co-workers.7b Of the three Ni2+ ions in the vertex in 2, one
is coordinated by two nitrogen atoms from one en ligand and
four oxygen atoms with one from water and three from PW9, the
other two are coordinated by two nitrogen atoms from one en
ligand and four oxygen atoms with one from the carboxylate of
HPA and three from PW9 respectively. Of the three Ni2+ ions in
the middle of the edge, one is coordinated by six oxygen atoms
with five from PW9 and one from a terminal aqua ligand, the
other two are coordinated by six oxygen atoms with five from
PW9 and one from the carboxylate of the HPA ligand. The bond
lengths of Ni–O, Ni–N, W–O and P–O are 1.992(7)–2.304(8),
2.018(11)–2091(8), 1.689(9)–2.504(8), and 1.500(9)–1.570(7) Å
respectively, comparable to those in the nickel substituted POMs
Rigaku R-AXIS RAPID IP diffractometer at 173 K for 1 and 2
on an Oxford Gemini S Ultra CCD area detector at 173 K for 3.
Absorption corrections were applied by using the analytical
program Tompa-analytical for 1 and 2, and multiscan program
CrysAlis Red for 3. The structures were solved by direct
methods, and non-hydrogen atoms were refined anisotropically
by least-squares on F2 using the SHELXTL program.13 The
SQUEEZE program was used to squeeze out the disordered
solvent molecules for 1 and 2, and part of the disordered water
molecules for 3.13 The hydrogen atoms of organic ligands were
generated geometrically (C–H, 0.96 Å; N–H, 0.90 Å). Crystal
data as well as details of the data collection and refinement for
the compounds are summarized in Table 1. Selected bond dis-
tances for the compounds are shown in Section S2 (ESI†)
Results and discussion
Single-crystal structural analysis reveals that 1 crystallizes in the
space group C2/m. The asymmetric unit in the core of the cluster
in 1 contains half a Ni6PW9 and Ni5PW9 units. The structure of
the cluster in 1 can be viewed as Ni6PW9 and Ni5PW9 units
linked by a μ3-O bridge and two IDA2− ligands as shown in
Fig. 1. Structurally, the Ni6PW9 unit is similar to that reported
by Yang and coworkers,7b that is, the six Ni2+ ions are arranged
Ni20 and Ni12.7c The separations of Ni⋯Ni are 2.968 to
7a
9872 | Dalton Trans., 2012, 41, 9871–9875
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Table 1 Crystal data and details of the data collection and refinement for compounds 1 to 3
Complex
1
2
3
Formula
Mr
T/K
C24H103O99N15P2W18Ni12
6261.97
173(2)
C18H79O56N8PW9Ni6
3341.56
173(2)
C18H70O60N9Cl2PW9Ni6
3481.61
173(2)
Cryst syst
Space group
a/Å
b/Å
c/Å
Monoclinic
C2/m
Orthorhombic
Pna21
22.325(5)
20.827(4)
13.671(3)
90
6357(2)
4
3.492
Orthorhombic
Cmc21
19.698(5)
19.032(5)
20.289(5)
90
7606.1(3)
4
3.040
38.794(8)
20.940(4)
17.201(3)
105.63(3)
13 457(5)
4
3.091
17.071
13 580/743
3.09–26.00
8498
β (°)
V/Å3
Z
Dc/g cm−3
μ/mm−1
Data/params
θ (°)
18.089
15.196
12 083/766
3.06–26.00
10 988
0.0596
0.1519
6370/467
2.93–26.00
5712
0.0456
0.0943
Obsd reflns
R1 [I > 2σ(I)]a
wR2 (all data)b
0.0885
0.2516
2 2
2 2
a R1 = ∑kFo| − |Fck/∑|Fo|. b wR2 = {∑[w(Fo2 − Fc ) ]/∑[w(Fo ) ]}1/2
.
3.169 Å, comparable to those in Ni6PW9 reported previously.7b
Owing to the very similar synthetic conditions for 1 and 2, the
structural differences between 1 and 2 indicate that the IDA2−
ligand plays a key role in the formation of the cluster 1.
It was mentioned that, although introducing IDA2− ligand is
of key importance for the formation of 1, further investigation
shows that the amount of IDA2− ligand used in the synthesis is
another important factor influencing the formation of 1. When
the amount of the IDA2− ligand used in the synthesis is
2.5 mmol, instead of 2.0 mmol as described for 1, compound
3 [Ni6PW9O34(H2IDA)2(HIDA)(OH)3(Hen)3]·Cl2·(H2O)11 was
obtained. Single-crystal analysis reveals that 3 crystallizes in the
space group Cmc21. The asymmetric unit in 3 contains half a
Ni6PW9 and one HIDA− ligand and half a H2IDA ligand. Struc-
turally, the Ni6 cluster in 3 is very similar to the Ni6PW9 unit of
1, except the μ3-O bridge linked to the Ni5PW9 in 1 is replaced
by monodentate coordinated Hen+ ligand as shown in Fig. 2b.
The bond lengths of Ni–O, Ni–N, W–O and P–O are 1.962(8)–
2.205(11), 2.032(16)–2.151(18), 1.693(8)–2.529(10), and
1.536(11)–1.562(8) Å respectively, are comparable to those in
Fig. 1 (a) Structure of [Ni11(PW9)2(IDA)3(en)2(Hen)2(OH)6]6− in 1.
(b) Ball-and-stick representation of [Ni11(IDA)3(en)2(Hen)2(OH)6]18+ in
1. WO6: green; PO4: purple; NiO6, NiO5N and NiO4N2: cyan, Ni: cyan,
O: red, N: blue, C: gray. Hydrogen atoms are omitted for clarity. (c)
Coordination modes of H2IDA ligand in 1.
the nickel substituted POMs Ni20 and Ni12.7c The separations
7a
of Ni⋯Ni are 3.068 to 3.166 Å, comparable to those in 2.
Thermal analysis
The TGA experiments were carried out for 1 to 3 in a flow of air
with a heating rate of 10 °C min−1 from 30 °C to 800 °C (Fig. 3
(a)–(c)). For 1, the weight loss in the temperature range from
30 °C to 200 °C corresponds to the removal of seven lattice
water molecules and two lattice en molecules per formula unit
(observed, 3.42%; calcd 3.86%). The remaining two stages
(in the ranges 300 °C to 450 °C and 550 °C to 700 °C) are
mainly attributed to the loss of the H2IDA ligands, four en mole-
cules, six coordinate water molecules and one P2O5 molecule
per formula unit (observed, 14.03%; calcd 14.15%). Assuming
that the residue corresponds to WO3 and NiO, the observed
Fig. 2 (a) Structure of [Ni6PW9(OH)3(HPA)2(en)3] cluster in 2; (b)
structure [Ni6PW9(H2IDA)2(HIDA)(OH)3(Hen)3]2+ in 3. WO6: green;
PO4: purple; Ni: cyan, O: red, N: blue, C: gray. Hydrogen atoms are
omitted for clarity.
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Fig. 4 Temperature dependence of the χMT at 1000 Oe, amaranth: 1;
red: 2; and blue: 3.
Fig. 3 TG curves from room temperature to 800 °C (a) for 1, (b) for 2
and (c) for 3.
residual weight 82.55% is in good agreement with the calculated
value of 81.99%.
The TGA curves of 2 and 3 show similar weight loss pro-
cesses to that of 1. The weight loss (observed, 6.05% for 2,
7.51% for 3) from 30 °C to 200 °C corresponds to the removal
of thirteen lattice water molecules for 2 (calcd 6.91%) and
eleven lattice water and two hydrochloric acid molecules for 3
(calcd 7.78%). The second weight loss (observed, 11.46% for 2,
13.25% for 3) from 300 °C to 450 °C is assigned to the removal
of two HPA ligands and three en molecules for 2 (calcd
11.32%), the removal of three H2IDA ligands and three en mol-
ecule for 3 (calcd 13.79%). The third weight loss (observed,
4.79% for 2, 5.23% for 3) from 550 °C to 700 °C is mainly
attributed to the loss of one P2O5 molecule and six water mol-
ecules from Ni(OH)2 (calcd 5.35% for 2, 5.22% for 3). The
observed residual weight of 77.70% for 2 and 74.01% for 3 is in
agreement with the calculated value of 76.42% for 2 and
73.21% for 3 respectively.
Fig. 5 Cyclic voltammograms of 1–3 in 2 × 10−4 M in pH = 4.3
(0.4 M CH3COONa + CH3COOH). The scan rate was 10 mV s−1
,
the working electrode was GC, and the reference electrode was SCE.
(1: blue; 2: red; 3: green).
Magnetic properties
The dc magnetic susceptibility for 1 to 3 was measured in the
temperature range of 2.0 to 300 K under an applied magnetic
field of 1000 Oe. The χMT vs. T plots are given in Fig. 4. The
χMT products of 1, 2 and 3 at room temperature is 14.31, 8.40
and 8.55 cm3 mol−1 K per formula unit, respectively, which are
expected for eleven, six and six uncoupled high-spin Ni2+ ion
with g > 2.7c With the decrease of the temperature, the χMT
values of 1 continuously increase and reach 19.1 cm3 mol−1 K at
25 K, indicating that intramolecular ferrimagnetic interactions
are dominant between Ni(II) centers in the Ni11 core. Below
25 K, the χMT values quickly drop to 5.7 cm3 mol−1 K at 2.0 K,
probably as a result of the presence of magnetic anisotropy
(zero-field splitting of the ground state) or weak antiferromag-
netic intra/inter-complex interactions. The magnetic suscepti-
bility of 2 and 3 is similar to that reported by Yang and co-
workers,7b indicating that intramolecular ferromagnetic inter-
actions exist between Ni(II) centres in the Ni6 core. The magnetic
interactions in 1 are different from those in 2 and 3 which may
be related to the longer Ni⋯Ni separations between the neigh-
bour Ni2+ ions in 1 (separations of Ni⋯Ni are: 2.991(0) to 3.609
(1) Å in 1, 2.974(0) to 3.170(1) Å in 2, 3.070 to 3.167 Å in 3).
Electrochemistry
Fig. 5 shows the typical cyclic voltammetric behavior of 1–3 in
the pH = 4.3 (0.4 M CH3COONa + CH3COOH) buffer solution
at different scan rates. Two quasireversible redox peaks (−0.721 V
and −0.889 V for 1, −0.725 V and −0.893 V for 2, −0.723 V
and −0.892 V for 3) were respectively observed for the three
compounds in the potential range from −0.4 to −1.0 V. The
cyclic voltammograms of the three compounds are very similar
in shape and are similar to the nickel substituted POMs.7f,g
Based on the previous literature,7f the peak at about −0.72 V cor-
responds to the redox of the WVI in the compounds 1 to 3.
9874 | Dalton Trans., 2012, 41, 9871–9875
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In conclusion, three nickel substituted POMs of [Ni(H2O)6]-
[Ni11(PW9O34)2(IDA)3(en)2(Hen)2(OH)6]·(H2O)7·(H2en)2, [Ni6-
PW9O34(HPA)2(OH)3(en)3(H2O)2]·(H2O)13 and [Ni6PW9O34-
(H2IDA)2(HIDA)(OH)3(Hen)3]·Cl2·(H2O)11 have been prepared.
Based on their structure and synthetic condition differences, we
revealed that introducing the polycarboxylate ligand of IDA2−
into POMs would favor the formation of high-nuclearity nickel
substituted POMs. Magnetic study shows that compound 1 exhi-
bits dominantly ferrimagnetic interactions within Ni11 core,
while compounds 2 and 3 show dominantly ferromagnetic inter-
actions within the Ni6 core. Thus, the present work provides a
new synthetic route to high-nuclearity metal substituted POMs.
Acknowledgements
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We thank the 973 Project from MSTC (Grant No
2012CB821704) and the NNSFC (Grant Nos. 20825103,
90922031 and 21021061) for the financial support.
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Dalton Trans., 2012, 41, 9871–9875 | 9875