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Template synthesis of {(MoV2O4)(O3PCH2PO3)}n

clusters (n ⴝ 3, 4, 10): solid state and solution studies
Charlotte du Peloux, Anne Dolbecq, Pierre Mialane,* Jérôme Marrot and Francis Sécheresse
Laboratoire de Physico-Chimie des Solides Moléculaires, Institut Lavoisier, UMR 8637,
Université de Versailles Saint-Quentin, 45 Avenue des Etats-Unis, 78035 Versailles Cedex,
France. E-mail: mialane@chimie.uvsq.fr
Received 26th January 2004, Accepted 24th February 2004
First published as an Advance Article on the web 19th March 2004

The influence of three exogenous ligands (acetate, formate and carbonate) on the condensation process of the
[Mo2O4]2⫹ dioxocation with the [O3PCH2PO3]4⫺ group has been investigated. Four cyclic or bicyclic compounds
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have been isolated and characterized by X-ray diffraction studies. Two closely related acetato and formato ovoidal
duodecanuclear compounds, Na24[Na4(H2O)6{(Mo2O4)10(O3PCH2PO3)10(CH3COO)8(H2O)4}]ⴢ103H2O (1) and
Na28[Na2{(Mo2O4)10(O3PCH2PO3)10(HCOO)10}]ⴢ110H2O (2), respectively, have been obtained. Their structures
can be described as two interconnected nonequivalent wheels, delimiting a large cavity. When the condensation is
performed in similar conditions but replacing carboxylato groups by carbonato ligands, the ellipsoidal octanuclear
Na11[Na(H2O)2{(Mo2O4)4(O3PCH2PO3)4(CO3)2}]ⴢ70H2O (3) compound is isolated. 31P NMR spectroscopic studies
have shown that complexes 1 and 3 are stable in solution at room temperature. Nevertheless, on heating an aqueous
solution of 3, the Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)]ⴢ18H2O (4) complex, free of carbonato groups, is obtained.
4 is a hexanuclear MoV wheel encapsulating a tetrahedral [MoVIO4]2⫺ anion. Its rational synthesis using a controlled
MoV/MoVI ratio is also presented.

Polyoxometalates (POMs) continue to be extensively studied for Experimental

their potential applications in catalysis 1 or medicine,2 but also
in various applied physical sciences due to their optical 3 or
magnetic 4 properties. The phosphomolybdenum family con-
stitutes the older class of polyanions, and the [PMo12O40]3⫺
Keggin complex,5 formed of twelve MoVI ions around a central
phosphato group, has been the first structurally characterized
POM. This anion can be reduced chemically or electro-
chemically to lead to mixed-valent MoVI/MoV species.6 More
recently, fully reduced MoV/phosphato compounds have been
characterised,7 the condensation in solution of MoV ions and
phosphato ligands leading mainly to extended frameworks
based on the [P4Mo6O31]12⫺, [P4Mo4O24]8⫺ or [P4Mo6O32]14⫺
building units. The diphosphato hetero-group [P2O7]4⫺ can
also react with molybdenum ions to give molecular POM
entities. Indeed, Kortz and Pope have characterised three
polyoxomolybdate complexes, where pyrophosphato ligands
are encapsulated in a MoVI ion matrix, the [P2O7]4⫺/MoVI
ratio being 1 : 6, 1 : 15 and 1 : 18.8 Finally, our group has
reported very recently the first MoV/pyrophosphate cluster.9
However, there is a limited number of characterised
molybdenum/pyrophosphate species. This can be tentatively
explained by the fact that pyrophosphato ligands are easily
hydrolysed to monophosphate groups in the presence of
molybdenum ions.10 Moreover, it has been shown that
MoV is a more efficient hydrolytic catalyst than MoVI. Then,
the use of the closely related organophosphonato ligand
[O3PCH2PO3]4⫺, stable toward hydrolysis, can represent an
alternative way to prepare [O3PXPO3]4⫺/molybdenum
systems. To date, only two methylenediphosphonate com-
pounds have been isolated, the fully oxidised [Mo6O18(O3-
PCH2PO3)(H2O)4]4⫺ anion 11 and the mixed-valent [MoV6-
MoVIO16(O3PCH2PO3)3]8⫺ compound.12 In both cases, the
DOI: 10.1039/ b401250j
Synthesis of Na24[Na4(H2O)6{(Mo2O4)10(O3PCH2PO3)10-
(CH3COO)8(H2O)4}]ⴢ103H2O (1)
0.242 g (1 mmol) of Na2MoO4ⴢ2H2O was dissolved in 10 mL of
4 M sodium acetate buffer (pH = 4.67) and 24 µL (0.49 mmol)
of N2H4ⴢH2O and 87 mg (0.5 mmol) of H4P2CH2O6 were
added. The obtained green solution turned progressively to
red while stirring for 3 h at 60 ⬚C. The solution was then allowed
to cool to room temperature and left to evaporate. Orange
parallelepipedic crystals were collected by filtration after one
week. Yield: 0.2 g (54% based on Mo). IR (KBr pellet, ν/cm⫺1):
1553 (m), 1454 (m), 1418 (m), 1182 (m), 1155 (m), 1105 (m),
1052 (s), 1011 (s), 944 (s), 805 (w), 743 (w), 681 (w), 571 (m), 519
(m), 485 (m), 462 (m). Na28H270Mo20P20C26O229: calc. Mo 25.82,
P 8.34, C 4.20, Na 8.67; found: Mo 25.77, P 8.36, C 5.29, Na
9.55%.13
Synthesis of Na28[Na2{(Mo2O4)10(O3PCH2PO3)10(HCOO)10}]ⴢ
110H2O (2)
0.242 g (1 mmol) of Na2MoO4ⴢ2H2O was dissolved in 5 mL of
4 M formic acid, and 24 µL (0.49 mmol) of N2H4ⴢH2O was
added. The obtained solution was stirred for 3 h while heating
at 60 ⬚C. 87 mg (0.5 mmol) of H4P2CH2O6 was then added and
the pH increased to 3.7 by addition of saturated aqueous
sodium hydroxide. The solution was then cooled to room tem-
perature and left to evaporate. Red cubic crystals were collected
by filtration after two days. Yield: 0.119 g (31% based on Mo).
IR (KBr pellet, ν/cm⫺1): 1583 (m), 1390 (m), 1353 (m), 1184 (m),
1162 (m), 1109 (s), 1056 (s), 1007 (s), 952 (s), 819 (w), 804 (w),
787 (w), 741 (w), 574 (m), 490 (m). Na30Mo20P20C20O230H250:
calc. Mo 25.93, P 8.37, C 3.25, Na 9.32; found: Mo 25.27,
P 7.90, C 4.14, Na 10.24%.13

structure consists of six coplanar molybdenum ions forming

a wheel. We report here on the condensation process of the
[Mo2O4]2⫹ dioxocation with the [O3PCH2PO3]4⫺ group in the
presence of templating exogenous ligands (acetate, formate
or carbonate). Four cyclic or bicyclic compounds has been
characterised by X-ray diffraction studies, and their behaviour
in solution has been investigated.
Synthesis of Na11[Na(H2O)2{(Mo2O4)4(O3PCH2PO3)4(CO3)2}]ⴢ
70H2O (3)
0.61 g (2.5 mmol) of Na2MoO4ⴢ2H2O was dissolved in 12.5 mL
of 4 M hydrochloric acid, and 30.5 µL (0.63 mmol) of N2H4ⴢ
H2O was added. The pH of the solution was then increased to

This journal is © The Royal Society of Chemistry 2004 Dalton Trans., 2004, 1259–1263 1259
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Table 1 Crystallographic data for Na24[Na4(H2O)6{(Mo2O4)10(O3PCH2PO3)10(CH3COO)8(H2O)4}]ⴢ103H2O (1), Na28[Na2{(Mo2O4)10(O3PCH2-

PO3)10(HCOO)10}]ⴢ110H2O (2), Na11[Na(H2O)2{(Mo2O4)4(O3PCH2PO3)4(CO3)2}]ⴢ70H2O (3) and Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)]ⴢ18H2O (4)

1 2 3 4

Empirical formula Na28H270Mo20P20C26O229 Na30Mo20P20C20O230H250 Na12Mo8P8O118C6H152 Na8Mo7P6C3O52H42

Mr 7430.30 7400.06 3404.04 1951.68
Crystal system Monoclinic Monoclinic Monoclinic Monoclinic
Space group P21/n P2/m P21/c P21/n
a/Å 21.7983(1) 22.5992(1) 17.8486(3) 16.9461(3)
b/Å 23.1131(3) 21.8196(4) 14.1970(3) 13.5032(1)
c/Å 22.6727(3) 22.8168(4) 17.9916(4) 22.3135(3)
β/⬚ 97.792(1) 91.080(1) 117.980(1) 94.908(1)
V/Å3 11317.6(2) 11249.1(3) 4026.11(14) 5087.20(12)
Z 2 2 2 4
Dc/g cm⫺3 2.180 2.185 2.808 2.548
µ/mm⫺1 1.402 1.414 1.623 2.055
T /K 296(2) 296(2) 296(2) 296(2)
Data/parameters 29325/1437 29994/1511 10342/518 13218/714
R (> 2σ(I )) R1(Fo) a = 0.0554, R1(Fo) = 0.0858, R1(Fo) = 0.0317, R1(Fo) a = 0.0530,
wR2(Fo2) b = 0.1266 wR2(Fo2) b = 0.2459 wR2(Fo2) b= 0.0872 wR2(Fo2) b = 0.1344
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R (all data) R1(Fo) a = 0.1233, R1(Fo) a = 0.1553, R1(Fo) a = 0.0462, R1(Fo) a = 0.0871,
wR2(Fo2) b = 0.1562 wR2(Fo2) = 0.2914 wR2(Fo2) b = 0.0924 wR2(Fo2) b = 0.1512
a
R1 = Σ(|Fo| ⫺ |Fc|)/Σ|Fo|. b wR2 = [Σw(Fo2 ⫺ Fc2)2/Σw(Fo2)2]1/2.

1.5 with 1 M sodium carbonate solution and 0.25 g (1.25 mmol)
of H4P2CH2O6 was added. Finally, the pH was adjusted to pH 5
by addition of a 1 M sodium carbonate solution and the solu-
tion stirred for 3 h. The resulting red solution was then allowed
to evaporate at room temperature and red cubic crystals suit-
able for X-ray diffraction were collected by filtration after 4
days. Yield: 0.50 g (47% based on Mo). IR (KBr pellet, ν/cm⫺1):
1447 (s), 1397 (m), 1361 (sh), 1186 (s), 1162 (s), 1119 (m), 1052
(sh), 1031 (s), 955 (s), 930 (sh), 803 (m), 743 (m), 565 (m), 491
(m). Na12Mo8P8O118C6H152: calc. Mo 22.54, P 7.28, C 2.12, Na
8.10; found: Mo 22.90, P 7.15, C 2.11, Na 9.96%.
Synthesis of Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)]ⴢ18H2O (4)
0.242 g (1 mmol) of Na2MoO4ⴢ2H2O was dissolved in 10 mL of
4 M sodium acetate buffer (pH = 4.67), and 8 µL (0.16 mmol)
of N2H4ⴢH2O and 85 mg (0.45 mmol) of H4P2CH2O6 were
added. The obtained green solution turned progressively to red
while stirring for 3 h at 60 ⬚C. The resulting solution was cooled
to room temperature and left to evaporate. Red octahedral
crystals were collected by filtration after two weeks. Yield:
0.08 g (29% based on Mo). IR (KBr pellet, ν/cm⫺1): 1182 (m),
1161 (m), 1113 (w), 1058 (s), 1008 (s), 968 (s), 955 (s), 927 (w),
851 (m), 813 (s), 758 (w), 548 (w), 521 (w), 493 (w), 431 (w).
Na8Mo7P6C3O52H42: calc. Mo 34.41, P 9.52, C 1.85, Na 9.42;
found: Mo 35.04, P 9.35, C 2.09, Na 9.36%.
X-Ray crystallography
Intensity data collection was carried out with a Siemens
SMART three-circle diffractometer equipped with a CCD
detector using Mo-Kα monochromatized radiation (λ =
0.71073 Å). The absorption correction was based on multiple
and symmetry-equivalent reflections in the data set using
the SADABS program 14 based on the method of Blessing.15
The structures were solved by direct methods and refined by
full-matrix least squares using the SHELX-TL package.16
Disordered water molecules and sodium counter-ions have
been refined with partial occupancy factors. Crystallographic
data are given in Table 1. Selected bond distances are listed in
Table 2.
CCDC reference numbers 229664–229667.
See http://www.rsc.org/suppdata/dt/b4/b401250j/ for crystal-
lographic data in CIF or other electronic format.
NMR measurements
31
P NMR spectra were recorded on a Brüker AC-300 spectro-
meter operating at 121.5 MHz in 5 mm tubes. 31P chemical
shifts were referenced to the external usual standard 85%
H3PO4.
Elemental analysis
Elemental analyses were performed by the Service Central
d’Analyse Elémentaire, CNRS, 69390 Vernaison, France.
Infrared spectra
IR spectra were recorded on an IRFT Magna 550 Nicolet
spectrophotometer using the technique of pressed KBr pellets
at a resolution of 0.5 cm⫺1.
Results and discussion
Synthesis and solid state structures of complexes Na24[Na4(H2O)6-
{(Mo2O4)10(O3PCH2PO3)10(CH3COO)8(H2O)4}]ⴢ 103H2O (1),
Na28[Na2{(Mo2O4)10(O3PCH2PO3)10(HCOO)10}]ⴢ110H2O (2),
Na11[Na{(H2O)2(Mo2O4)4(O3PCH2PO3)4(CO3)2}]ⴢ70H2O (3)
and Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)]ⴢ 18H2O (4)
General considerations. Compounds 1, 2, 3 and 4 are based
on the dinuclear [MoV2O2(µ-O)2]2⫹ fragment. This cationic
species is obtained in solution by the chemical reduction of
sodium molybdate() by hydrazine. This reaction occurs
either in pure acidic solution or in carboxylate buffers. When
carboxylato solutions are used, the stoichiometric addition of
methylenediphosphonic acid can be effectuated before or after
the adjustment of the pH. In contrast, it is essential to raise the
pH to 1.5 before the addition of the polyphosphato ligand
when the reaction is performed in hydrochloric acid solution;
otherwise, an insoluble molybdenum hydroxide diphosphonato
compound is obtained. It should also to be noticed that the
use of an excess of methylenediphosphonato ligand has no
influence on the resulting products.
All these four compounds can be viewed as the condensation
of {MoV2O2(µ-O)2(O3PCH2PO3)} building units. A strict
orthogonality of the PV–PV and MoV–MoV axis is observed.
Due to the presence of a metal–metal bond, the average
Mo–Mo distance in a dinuclear unit is short (ca. 2.6 Å).
Each molybdenum ion is in a distorted octahedral environment,
with a terminal oxygen atom and two bridging oxo ligands.
Then, in a dinuclear fragment, the two molybdenum centres are
sharing an edge. Selected bond lengths and distances are given
in Table 2.
Compounds 1 and 2 are closely related to the previously
reported pyrophosphato compound Na24[Na4(H2O)6{(Mo2-
O4)10(P2O7)10(CH3COO)8(H2O)4}]ⴢ97H2O.9 1 and 2 are built up

1260 Dalton Trans., 2004, 1259–1263

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Table 2 Selected bond lengths (Å) for Na24[Na4(H2O)6{(Mo2O4)10(O3PCH2PO3)10(CH3COO)8(H2O)4}]ⴢ103H2O (1), Na28[Na2{(Mo2O4)10(O3PCH2-

PO3)10(HCOO)10}]ⴢ110H2O (2), Na11[Na(H2O)2{(Mo2O4)4(O3PCH2PO3)4(CO3)2}]ⴢ70H2O (3) and Na8[(Mo2O4)3(O3PCH2PO3)3(MoO4)]ⴢ18H2O (4)

1 2 3 4

MoV᎐O 1.674(5)–1.699(5) 1.631(7)–1.701(8) 1.677(2)–1.706(2) 1.682(2)–1.697(2)

MoV–OMo 1.929(4)–1.957(4) 1.916(6)–1.964(5) 1.917(2)–1.946(2) 1.9346(18)–1.9510(19)
MoV–OP 2.067(5)–2.5709(8) 2.051(6)–2.394(8) 2.039(2)–2.501(2) 2.0538(19)–2.5170(19)
MoVI–O – – – 1.709(7)–1.754(7)
MoV–MoV 2.5576(8)–2.5709(8) 2.5631(10)–2.5873(13) 2.5543(4)–2.5583(4) 2.5664(3)–2.5786(3)
P᎐᎐O 1.502(5)–1.514 (4) 1.484(8)–1.509(7) 1.497(2)–1.506(2) 1.491(2)–1.506(2)
P–OMo 1.526(5)–1.540(5) 1.515(5)–1.572(6) 1.533(2)–1.547(2) 1.534(2)–1.559(2)
P–C 1.790(8)–1.811(6) 1.775(8)–1.836(8) 1.802(4)–1.812(3) 1.800(3)–1.830(3)
Naencapsulated–O 2.313(8)–2.584(6) 2.453(6)–2.522(6) 2.291(3)–2.558(3) –

of two non-equivalent interconnected wheels (Fig. 1 and

Fig. 2). The larger one contains twelve MoV ions and the
smaller eight MoV centres. The wheels consist in the alternating
association of MoV pairs and diphosphonato groups.
Carboxylato ligands (acetato ligands in 1 and formato ligands
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in 2) are anchored to molybdenum dimers, connecting the

two MoV centers. In complex 1, two types of dimers are present,
the acetato {Mo2O4(CH3COO)} and the aquo {Mo2O4(H2O)2}
dinuclear units. The larger wheel is formed of four acetato and
two aquo dimers, while the smaller one is constituted of four
acetato dimers. In compound 2, all the dinuclear fragments are
linked to formato ligands, forming {Mo2O4(HCOO)} groups.
In both compounds, the carboxylato ligands are directed
toward the inside of the cavity for the larger wheel, whereas in
the smaller one they are directed toward the outside. The
junctions between the two wheels are ensured by four diphos-
phonato ligands. These wheels are nearly perpendicular, with
angles of 88.5(2) and 90.0(2)⬚ in 1 and 2, respectively, forming Fig. 2 Polyhedral and ball-and-stick representation of compound 2.
View highlighting the {Mo12} wheel with the bridging formato ligands
pointing toward the inside of the cavity.

an ovoidal cluster. The valence bond summations confirmed the

oxidation state of the molybdenum atoms and showed that the
diphosphonato ligands are fully deprotonated. Thus, complexes
1 and 2 are 28 and 30 negatively charged, respectively. For
both compounds, two sodium cations are localised at the
junctions of the two wheels, each alkaline ion connecting
four carboxylato dinuclear units through eight oxygen
atoms. In 1, two additional sodium ions are connected to
the two {(Mo2O4)(H2O)2} dimers via the aquo ligands. The
volume of the ovoidal cavity defined by these bicyclic clusters
is significantly greater in 2 than in 1 (264 and 130 Å3,
respectively).
Compound 3 contains four MoV dimers, and can be
described as the assembly of two tetrameric {(Mo2O4)2(O3-
PCH2PO3)} units related by an inversion centre (Fig. 3). In a
tetramer, the two dinuclear MoV units are connected via a µ3-O
and two µ2-O atoms of the η3-CO32⫺ ligand. The two tetrameric
units are linked by two diphosphonate ligands. The eight
molybdenum() atoms and the two carbonato ligands are
coplanar. This association leads to an octanuclear ellipsoidal
cluster, which encapsulates an octahedral {NaO4(H2O)2}
sodium ion.

Fig. 1 Polyhedral and ball-and-stick representations of compound 1.

Views emphasising (a) the {Mo8} wheel with the bridging acetato
ligands pointing toward the outside of the cavity and (b) the nearly
perpendicular connection between the {Mo12} and {Mo8} wheels and
the encapsulated Na⫹ cations. Medium grey octahedra, {MoVO6}; white
tetrahedra, {O3P(CH2)}; white cross-hatched spheres, C; medium grey
hatched spheres, Na; white spheres, OH2. Fig. 3 Polyhedral and ball-and-stick representation of compound 3.

Dalton Trans., 2004, 1259–1263 1261


Compound 4 crystallises as a sodium salt. This compound
has been previously synthesised under hydrothermal con-
ditions and isolated as water-insoluble ethylenediamine and
piperazine salts.12 Three corner-sharing MoV dimers, forming
a planar hexamolybdate wheel, encapsulate a central MoVI
tetrahedron (Fig. 4(a)). The MoVI ion is localised 0.78 Å above
the {Mo6} plan. Three diphosphonato ligands are anchored at
the periphery of the cyclic unit. Complex 4 can be compared
to the well-known [P4Mo6O31]12⫺ anion (Fig. 4(b)).17 The main
difference arises from the connection between dimers, which
are linked by an edge in the case of the monophosphato com-
pound, while the dinuclear fragments are sharing a corner in the
diphosphonato complex 4.
Published on 19 March 2004 on http://pubs.rsc.org | doi:10.1039/B401250J
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Fig. 4 Polyhedral and ball-and-stick representations of (a) the
molecular complex [MoV6MoVIO16(O3PCH2PO3)3]8⫺ (4) and (b) the
[P4Mo6O31]12⫺ wheel (from ref. 17). Medium grey octahedra, {MoVO6};
medium grey hatched tetrahedra, {MoVIO4}; white tetrahedra,
{O3P(CH2)} (a) or {PO4} (b).
NMR spectroscopy. The behaviour in solution of these
molecular compounds has been studied by 31P NMR at room
temperature. The spectrum of 1 in a 4 M acetate buffer solution
(Fig. 5(a)) exhibits three peaks of 2 : 1 : 2 relative intensities.
This clearly indicates that the solid state structure of this com-
pound is retained in solution. Indeed, we can attribute the low
field resonance peak found at 27.00 ppm to the diphosphonato
groups connecting the wheels, and the two peaks at higher
fields, close in chemical shift (25.51 and 25.28 ppm), to the
{O3PCH2PO3} groups constituting the smaller and the larger
wheel, respectively. When compound 1 is dissolved in a pure
water solution, the obtained 31P NMR spectrum (Fig. 5(b)) is
strikingly different, as only two peaks at 26.27 and 25.54 ppm
of relative intensities 1 : 2 could be observed. This new species
has not been structurally characterised to date. Nevertheless,
this contrasts with the behaviour of the analogous pyrosphos-
phato complex of compound 1. Indeed, in this case, a complete
hydrolysis of the [P2O7]4⫺ groups occurred in water, leading to
the [P4Mo6O31]12⫺ species and to free [PO4]3⫺ ligands. Moreover,
it should be noticed that the nature of the carboxylato ligand
structuring the double-wheel edifice is also crucial, as it has
been found that complex 2 is not stable either in formate buffer
solution or in water.
1262 Dalton Trans., 2004, 1259–1263
View Online
Fig. 5 31P NMR spectra at room temperature of (a) 1 in 4 M acetate
buffer, (b) 1 in pure water solution, (c) 3 in pure water solution and (d) 4
in pure water solution.
While compounds 1 and 2 evolve in pure water solution at
room temperature, the situation is different for compound 3, as
two peaks of equal intensities at 27.30 and 23.95 ppm were
observed (Fig. 5(c)), in agreement with the solid state structure
determined by X-ray crystallography. However, when a solution
of compound 3 is heated at 80 ⬚C for 1 h, the decomposition of
this complex occurs, and complex 4 is formed. This latter com-
pound is stable in aqueous media, whatever the temperature.
The 31P NMR spectrum (Fig. 5(d)) exhibits a doublet of
doublets at 25.46, 25.33, 24.68 and 24.55 ppm (J = 16.8 Hz),
with a second-order perturbation. This can be explained by
the non-equivalence of the two phosphorous atoms in a {O3-
PCH2PO3} group, due to the presence of a central [MoVIO4]2⫺
tetrahedron which prevents the plane containing the MoV
atoms to be a mirror plane.
Conclusion
Two duodecanuclear ovoidal complexes, 1 and 2, have been
characterised in both solution and in the solid state. Both com-
pounds define a large cavity. Its size is strongly dependent on
the carboxylato ligand used, the volume being twice as large for
the formato complex than for the acetato compound. Single
crystal diffraction studies have shown that no water molecules
are located in these cavities, suggesting their hydrophobic
character. It remains to be studied if such complexes are able to
accommodate small organic molecules. While compound 1 is
stable in acetate buffer, a new species is formed when either 1 or
2 are dissolved in pure water. Attempts to characterise the
obtained compound are under way. Compounds 1 and 2 can
be considered as inorganic cryptates, as two tightly bounded
octacoordinated sodium cations are found at the junction of
the two wheels. Characterization of related potassium salts have
failed to date. The templating role of the exogenous ligand on
the [MoV2O2(µ-O)2(O3PCH2PO3)]2⫺ condensation process is
clearly shown, as an octanuclear complex is obtained when
carbonato ligands are used instead of carboxylate. Complex 3
is stable in water at room temperature, but evolves when the
solution is heated to afford the mixed-valent complex 4, show-
ing that partial oxidation occurs in the presence of dioxygen. It

has been possible to isolate compound 4 in a relatively good
yield by working with a stoichiometric MoV/MoVI amount. The
nuclearity of these polyoxomolybdate clusters is then strongly
dependant on the templating agent used, and inclusion of vari-
ous ligands (such as oxalate, sulfite, dicarboxylate, etc. . .)
should allow the characterisation of new species with different
nuclearities and topologies.
References
1 (a) N. Mizumo and M. Misono, Chem. Rev., 1998, 98, 199; (b)
D. Sloboda-Rozner, P. L. Alsters and R. Neumann, J. Am. Chem.
Soc., 2003, 125, 5280.
2 (a) Polyoxometalates: From Platonic Solids to Anti-Retroviral
Activity, ed. M. T. Pope and A. Müller, Kluwer Academic
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