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Polyoxometalate (POM)-based, multi-functional, inorganicorganic, hybrid

compounds: syntheses and molecular structures of silanol- and/or siloxane
bond-containing species grafted on mono- and tri-lacunary Keggin POMs
Shotaro Aoki, Takayuki Kurashina, Yuhki Kasahara, Tadashi Nishijima and Kenji Nomiya*
Received 8th September 2010, Accepted 8th November 2010
DOI: 10.1039/c0dt01185a
Using 3-mercaptopropyltrimethoxysilane (HS(CH2 )3 Si(OMe)3 ) as a silane-coupling agent (SCA),
mono- and tri-lacunary Keggin polyoxometalate (POM)-based, multi-functional, inorganicorganic,
hybrid compounds, (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] EtN-1 (the 1 : 2 complex of a POM unit and
organosilyl groups), (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2 (the 1 : 3 complex) and
(Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3 (the 1 : 4 complex) were synthesized and
unequivocally characterized by elemental analysis, thermogravimetric and differential thermal analyses
(TG/DTA), FTIR, solid-state (29 Si and 31 P) CPMAS NMR, solution (29 Si, 31 P, 1 H and 13 C) NMR, and
X-ray crystallography. [Note: The moieties of their polyoxoanions are abbreviated simply as 13,
respectively.] The X-ray molecular structures of EtN-1 and BuN-3 were determined. In EtN-1, two
organic groups connected through a siloxane bond (SiOSi bond) were grafted on a mono-lacunary
site of a Keggin POM, whereas in BuN-3 four organic groups connected through siloxane bonds were
grafted on a tri-lacunary site of a Keggin POM. In BuN-2, three organic groups were grafted in the
form of silanol (SiOH) on a tri-lacunary site, i.e., in BuN-2 there was no siloxane bond. BuN-3 was
synthesized as BuN-3a and BuN-3b by two methods, respectively; (1) BuN-3a was obtained by a 1 : 1
molar-ratio reaction of BuN-2 and an SCA in CH3 CN, and (2) BuN-3b was prepared by a direct 1 : 4
molar-ratio reaction of a tri-lacunary Keggin POM and SCA in waterCH3 CN. X-Ray crystallography
revealed that BuN-3a is the same as BuN-3b. It is probable that BuN-2 is an intermediate in the
formation of BuN-3. Terminal SH groups in 13, as well as OH groups in 2, can be utilized for
immobilization of POMs and, also, as building blocks for the formation of novel hybrid compounds.

Introduction
Polyoxometalates (POMs) are discrete metal oxide clusters that
are of current interest as soluble metal oxides and for their
applications in catalysis, medicine, and materials science.1 The
preparation of POM-based materials is therefore an active eld
of research and, in particular, the combination of POMs with
organic molecules has brought about a variety of inorganic
organic hybrid materials.2 The introduction of organic groups
into POMs is an efcient technology to signicantly increase the
number of inorganicorganic hybrid compounds and to improve
their properties. Various types of Keggin POMs with organic
groups have been reported and the molecular structures of several
Department of Materials Science (present name Department of Chemistry),
Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293,
Japan
Electronic supplementary information (ESI) available: Synthesis of the
) and angles ( ) for EtN-1 and BuNPOM precursors; bond lengths (A
3a (Tables S1 and S2, respectively). CCDC reference numbers 790105 for
EtN-1and 790104 for BuN-3a. For ESI and crystallographic data in CIF
or other electronic format see DOI: 10.1039/c0dt01185a

This journal is The Royal Society of Chemistry 2011

compounds have been determined by X-ray crystallography. These

include [(PW9 O34 )2 (PhSnOH)3 ]12- ,3a [b-SiW9 O37 (PhSn)3 ]7- ,3b [(aSiW9 O34 )2 (BuSnOH)3 ]14- ,3b [(PW11 O39 )(PhPO)2 ]3- ,3c [(g-PW10 O36 )(t BuSiOH)2 ]3- ,3d [a-A-PW9 O34 (t BuSiO)3 (SiCH2 -CH CH2 )]3- ,3e
[a-A-PW9 O34 (t BuSiOH)3 ]3- and [a-B-AsW9 O33 (t BuSiOH)3 ]3- ,3f
[a-A-PW9 O34 (RSiO)3 (RSi)]3- (R = C2 H3 , CH3 , C2 H5 ),3g,h and
[a-SiW11 O39 {PhCH2 P(O)}2 ]4- .3i Proust et al. recently reported
Keggin POM-based organosilyl/germyl hybrids such as
[PW9 O34 (t BuSiO)3 Ge(CH2 )2 CO2 H]3- .3j
On the other hand, the molecular structures of Dawson POM-based inorganicorganic hybrid compounds such
as [a-P2 W15 O59 (PhSn)3 ]9- ,3a [{(C6 H6 )Ru(H2 O)}(a2 -P2 W17 O61 )]8- 4a
and [a2 -P2 W17 O61 {O(SiR)2 }]6- (organic groups with terminal
functional groups: R = Ph, C3 H6 SH, C3 H6 SCN 4b and
(CH2 )3 N+ Me3 ,4c and organic groups with terminal olens:
R = {(CH2 )3 OCO(CH3 )C CH2 }, {(CH2 )3 OCOCH CH2 } and
{CH CH2 }4d ) have been determined. Many compounds have
been prepared by reactions of an a2 -mono-lacunary Dawson POM [a2 -P2 W17 O61 ]10- with a silane-coupling agent (SCA),
such as RSiX3 (X = Cl, OMe, OEt), under acidic conditions. X-Ray crystallography has revealed that two organic
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chains connected through a siloxane bond (SiOSi bond)

were grafted onto an a2 -mono-lacunary site of a Dawson
POM. Very recently, by reactions of [a2 -P2 W17 O61 ]10- with tetrachlorosilane (without the addition of acids) or tetraethoxysilane (Si(OEt)4 : TEOS) under HCl-acidic conditions (pH 1),
the formation of a cyclic trimer, i.e., [{a2 -P2 W17 O61 (Si2 O)}3 (mO)3 ]18- , composed of three a2 -mono-lacunary Dawson POMs
connected through intra- and intermolecular siloxane bonds, was
conrmed.4e As other examples of the Dawson POM family,
Cronin et al. recently reported inorganicorganicinorganic
hybrid compounds, i.e., [{P2 V3 W15 O59 (OCH2 )3 CNHCO}2 ]12- and
[{P2 V3 W15 O59 (OCH2 )3 CCH2 }2 O]12- ,4f derived by grafting linear
bis(tris) ligands onto a V3 -capped WellsDawson-type POM
[P2 V3 W15 O62 ]9- . Many other inorganicorganic hybrid compounds, characterized by X-ray crystallography, can also be found
in the literature.5
From a practical point of view, the heterogenization or immobilization of POM-based acid and oxidation catalysts is expedient
owing to the ease of recycling and separation of these catalysts
from the reaction products. Some of the modied POMs with
organic functional groups, such as thiol, vinyl, and methacryl
groups, can be used as precursors for the immobilization of
POMs.2o,6 For example, for fuel-cell applications, the preparation
and characterization of a proton-conductive membrane using
[SiW11 O39 {(CH2 CHSi)2 O}]4- has been reported.6d In the platinum electrode of a fuel cell, which was modied with a Dawsontype inorganicorganic hybrid POM with a terminal SH group,
the catalytic activity was found to be enhanced.6e,f
In this work, to extend the chemistry of POM-based inorganic
organic hybrid compounds containing multi-functional groups, we
examined the reactions of mono- and tri-lacunary Keggin POMs
with 3-mercaptopropyltrimethoxysilane (HS(CH2 )3 Si(OMe)3 ) as
the SCA. Three novel hybrid compounds, which have been
unreported so far, i.e., (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}]
EtN-1 (the 1 : 2 complex of a POM unit and organosilyl group), (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2 (the
1 : 3 complex with a silanol form) and (Bu4 N)3 [A-aPW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3 (the 1 : 4 complex
with siloxane bonds) were synthesized and unequivocally characterized. The 1 : 4 complex (BuN-3a) was prepared by a reaction
of the 1 : 3 complex (BuN-2) with one mole of SCA in CH3 CN
and the same compound (BuN-3b) was also prepared by a direct
1 : 4 molar-ratio reaction of a tri-lacunary Keggin POM with an
SCA in waterCH3 CN. The 1 : 3 complex with both terminal thiol
groups and silanol groups is a building block, not only for the 1 : 4
complex formation, but also for other new hybrid complexes.
Herein, we report full details of the synthesis and unequivocal
characterization of EtN-1, BuN-2 and BuN-3, and the molecular
structures of EtN-1 and BuN-3.

Results and discussion

Synthesis and compositional characterization
The tetraethylammonium salt of the 1 : 2 complex of
a Keggin POM unit : an organic group, i.e., (Et4 N)3 [aPW11 O39 {(HS(CH2 )3 Si)2 O}] EtN-1, was prepared by a 1 : 2
molar-ratio reaction under HCl-acidic conditions (pH 0.5) of
a mono-lacunary a-Keggin POM, K7 [a-PW11 O39 ]13H2 O, with
1244 | Dalton Trans., 2011, 40, 12431253

3-mercaptopropyltrimethoxysilane (HS(CH2 )3 Si(OMe)3 ) as the

SCA, in a solvent mixture of CH3 CNH2 O (200/100 v/v). Yellow
rod crystals were obtained in 54.1% yield (1.07 g scale) by slow
evaporation of a mixed solution of 1 M aqueous HCl solution
acetonitrile containing the powder sample once isolated. The
tetrabutylammonium salt of 1 was also prepared, but it was
highly soluble in CH3 CN and difcult to crystallize (see also
Experimental section).
The formation of polyoxoanion 1 can be represented in eqn (1):
2 HS(CH2 )3 Si(OMe)3 + [a-PW11 O39 ]7- + 4 H+ + H2 O
[a-PW11 O39 {(HS(CH2 )3 Si)2 O}]3- 1 + 6 MeOH

(1)

The composition and formula of EtN-1 were consistent with

complete elemental analysis, TG/DTA, FTIR, solid-state (29 Si,
31
P) CPMAS NMR and solution (29 Si, 31 P, 1 H and 13 C) NMR
spectroscopy, and X-ray crystallography. The sample for elemental
analysis was dried at room temperature under a vacuum of 10-3
10-4 torr overnight. All elements (C, H, N, O, P, S, Si, and W) were
observed for a total analysis of 99.84%, including oxygen, and
the found data were in good agreement with the calculated values
for the formula with 3 Et4 N+ cations (see Experimental section).
Weight loss for EtN-1 during the course of drying overnight
before analysis was negligible, indicating no solvated molecules,
which was also conrmed by TG/DTA measurements performed
under atmospheric conditions. In the 1 : 2 complex or EtN-1, two
organic groups were connected through siloxane bonds in a monolacunary site of a Keggin POM.
The tetrabutylammonium salt of the 1 : 3 complex of
a Keggin POM unit : the organic group, i.e., (Bu4 N)3 [APW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2, was prepared by a 1 : 3 molarratio reaction under HCl-acidic conditions of a tri-lacunary
Keggin POM, Na9 [A-PW9 O34 ]15H2 O, with HS(CH2 )3 Si(OMe)3
in a CH3 CN solution containing Bu4 NBr. A pink powder sample
was obtained in 41.5% yield (2.55 g scale) by reprecipitation
with cold methanol, but pure crystals of this compound were
not obtained. As related compounds, 1 : 3 complexes with terminal bulky groups, e.g., [a-A-PW9 O34 (t BuSiOH)3 ]3- and [a-BAsW9 O33 (t BuSiOH)3 ]3- ,3f have been characterized by X-ray crystallography. The formation of polyoxoanion 2 can be represented
in eqn (2):
3 HS(CH2 )3 Si(OMe)3 + [A-PW9 O34 ]9- + 6 H+ + 3 H2 O
[A-PW9 O34 (HS(CH2 )3 SiOH)3 ]3- 2 + 9 MeOH

(2)

The composition and formula of BuN-2 were determined by

elemental analysis, TG/DTA, FTIR, and solid-state (29 Si and
31
P) CPMAS NMR and solution (29 Si, 31 P, 1 H and 13 C) NMR
spectroscopy. This compound was the 1 : 3 complex of a trilacunary Keggin POM unit : an organic group, in which three
silanol groups remained and no siloxane bond was present.
Compound BuN-2 in solution showed a tendency to gradually
decompose and change to a formation of the 1 : 4 complex which
contains siloxane bonds or BuN-3. Addition of an aqueous HCl
solution promoted the formation of BuN-3. It is probable that
BuN-2 acts as an intermediate in the formation of BuN-3.
The tetrabutylammonium salt of the 1 : 4 complex of
a Keggin POM unit : an organic group, i.e., (Bu4 N)3 [A-aPW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3, was prepared by
two methods: (1) one (BuN-3a) was obtained by a reaction of
BuN-2 with an SCA in CH3 CN, and (2) the other (BuN-3b) was
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by a direct reaction of a tri-lacunary Keggin POM with an SCA

in waterCH3 CN.
(1) By a 1 : 1 molar-ratio reaction under HCl-acidic conditions
of BuN-2 with HS(CH2 )3 Si(OMe)3 in CH3 CN, colorless granular
crystals of BuN-3a were obtained in 45.5% yield (0.14 g scale). The
formation of polyoxoanion 3a can be represented in eqn (3):

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HS(CH2 )3 Si(OMe)3 + [A-PW9 O34 (HS(CH2 )3 SiOH)3 ]3- 2

(3)
[A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)]3- 3a + 3 MeOH
The composition and formula of BuN-3a were determined by
elemental analysis, TG/DTA, FTIR, solution (29 Si, 31 P, 1 H and 13 C)
NMR spectroscopy and X-ray crystallography. This compound
was the 1 : 4 complex of a tri-lacunary Keggin POM unit : an
organic group, in which there was no silanol group and all organic
groups were linked through siloxane bonds. Using a reaction
analogous to eqn (3), i.e., from a reaction of Cl3 Ge(CH2 )2 CO2 H
and [PW9 O34 (t BuSiOH)3 ],3f Proust et al. very recently reported
the formation of POM-based organosilyl/germyl hybrids such as
[PW9 O34 (t BuSiO)3 Ge(CH2 )2 CO2 H]3- .3j
(2) The tetrabutylammonium salt of the 1 : 4 complex, BuN3b, was also prepared by a direct 1 : 4 molar-ratio reaction at
80 C under HCl-acidic conditions of a tri-lacunary Keggin POM
with HS(CH2 )3 Si(OMe)3 in a solvent mixture of CH3 CNwater
(150/50 v/v). By slow evaporation, colorless granular crystals
(BuN-3b) were obtained in 49.7% yield (1.70 g scale), which
were characterized by complete elemental analysis, TG/DTA,
FTIR, solution (31 P, 1 H and 13 C) NMR spectroscopy and X-ray
crystallography. A pure powder sample was also obtained in 48.8%
yield (1.67 g scale) by washing the crude product sample with
acetonitrile at room temperature. Using this sample, solid-state
(29 Si, 31 P) CPMAS NMR spectra were measured.
The formation of polyoxoanion 3b can be represented in eqn
(4):
4 HS(CH2 )3 Si(OMe)3 + [A-PW9 O34 ]9- + 6 H+ + 3 H2 O
(4)
[A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)]3- 3b + 12 MeOH
In the overall reaction (4), the rate-determining step is a reaction
process of BuN-2 formed in solution with an SCA, or eqn (3).
X-Ray crystallography revealed that 3a was the same as 3b (both
are called 3). The key points in the synthesis of 3b were the choice
of the solvent system, the acidity of the reaction system and the
temperature, because the formation process of 3 from 2, i.e., eqn
(3), is slow. In the synthesis of BuN-3b, a tri-lacunary Keggin POM
precursor solid was added to the HCl-acidic aqueous medium with
a small portion of the precursor, because the precursor readily
decomposes in water.
The FTIR spectra, measured in KBr disks, showed vibrational
bands with medium intensity due to the SH groups at 2573 cm-1 for
EtN-1, 2567 cm-1 for BuN-2, 2565 cm-1 for BuN-3a and 2566 cm-1
for BuN-3b, and intense bands due to the SiOSi (siloxane
bonding) groups at 1111 cm-1 for EtN-1, 1122 cm-1 for BuN-3a,
and 1121 cm-1 for BuN-3b. In the FTIR spectra (Fig. 1), PO
vibrational bands of the mono-lacunary Keggin POM framework
at 1066, 1055, 1034 cm-1 for EtN-1 and those of the tri-lacunary
Keggin POM framework at 1099, 1036, 1005 cm-1 for BuN-2,
1039, 1001 cm-1 for BuN-3a and 1038, 1001 cm-1 for BuN-3b,
were observed, in addition to their characteristic Keggin WO
vibrational bands.7
This journal is The Royal Society of Chemistry 2011

Fig. 1 FTIR spectra in the polyoxoanion region (1800400 cm-1 ),

measured as KBr disks, of (a) (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}]
EtN-1, (b) (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2, and (c)
(Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3a.

Molecular structures of 1 and 3

Yellow rod crystals of EtN-1 were obtained by slow evaporation of
a solution of yellowwhite powder dissolved in a mixed CH3 CN
HCl-acidic aqueous medium at room temperature. They belong
to the monoclinic P2(1)/n space group. The crystals of EtN-1
contained a discrete polyoxoanion and three tetraethylammonium
cations, but no solvated molecules. The composition and formula
of EtN-1 were determined by complete elemental analysis and
TG/DTA analysis. The structure analysis of EtN-1 revealed that
two organic chains connected through a siloxane bond were
supported on the mono-lacunary site of a Keggin POM [aPW11 O39 ]7- . Three tetraethylammonium cations were identied.
The molecular structure, its polyhedral representation, and the
partial structure around the siloxane bond are shown in Fig. 2a
) and angles ( ) around the siloxane
2c. Selected bond lengths (A
) and
bond in 1 are given in Table 1, while other bond lengths (A
angles ( ) [range] for 1 (Table S1) are deposited in the ESI.
The crystallographically imposed symmetry on 1 is a 2-fold
axis that goes through the O35, P1, W3 and O5 atoms (Fig. 2a).
The molecular structure of 1 is depicted by a 2-fold disordered
model, which has been detailed in the X-ray crystallography
of [PW11 O39 (PhPO)2 ]3- .3c In 1, half of the molecules in the
crystal lattice are in the orientation shown in Fig. 2a and half
are in the orientation generated by the C 2 operation. The 2fold disorder contributes to the size of the thermal ellipsoids.
Despite the disorder in 1, the atom connectivity and mode of
Dalton Trans., 2011, 40, 12431253 | 1245

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) and angles ( ) around the siloxane
Table 1 Selected bond lengths (A
bond in 1

Bond lengths/A

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Si(1)O(29)
Si(1)O(40)
Si(1)O(35)
Si(1)C(1)
C(1)C(2)
C(2)C(3)
C(3)S(1)

1.621(15)
1.614(14)
1.624(14)
1.84(2)
1.57(3)
1.43(3)
1.84(3)

Si(2)O(30)
Si(2)O(36)
Si(2)O(35)
Si(2)C(4)
C(4)C(5)
C(5)C(6)
C(6)S(2)

1.620(15)
1.594(14)
1.638(15)
1.83(2)
1.79(4)
1.27(3)
1.85(3)

108.7(8)
109.5(8)
106.8(7)
109.5(8)
109.7(9)
112.5(9)
113.3(15)
113(2)
113.0(18)
128.1(8)

O(30)Si(2)O(35)
O(30)Si(2)O(36)
O(36)Si(2)O(35)
O(35)Si(2)C(4)
O(30)Si(2)C(4)
O(36)Si(2)C(4)
Si(2)C(4)C(5)
C(4)C(5)C(6)
C(5)C(6)S(2)

107.7(8)
107.9(8)
108.7(8)
110.9(9)
111.9(10)
109.7(9)
113.1(14)
104(2)
107(2)

Bond angles/
O(29)Si(1)O(35)
O(29)Si(1)O(40)
O(40)Si(1)O(35)
O(35)Si(1)C(1)
O(29)Si(1)C(1)
O(40)Si(1)C(1)
Si(1)C(1)C(2)
C(1)C(2)C(3)
C(2)C(3)S(1)
Si(1)O(35)Si(2)

attachment of the organic groups to the lacunary anion are

unequivocal. The two organic groups connected through the
siloxane bond can be treated as approximately equivalent groups
due to the disorder, resulting in the approximate C s symmetry of
the overall polyoxoanion molecular structure. The bond lengths
and angles of the Si(1)O(35)Si(2) bond [1.624(14)1.638(15)
, 128.1(8) ] and the lengths of the four SiO bonds [Si(1)
A
O(40), Si(1)O(21), Si(2)O(36), Si(2)O(30); 1.594(14)1.621(15)
] coordinated to the four oxygen atoms in the lacunary site
A
in 1 can be compared with those of the previously reported
Dawson POM analog, i.e., [a2 -P2 W17 O61 {(HS(CH2 )3 Si)2 O}]6- [Si
, angle 126.3(9) : the
OSi bond lengths 1.631(14)1.637(15) A
].4b
four SiO bond lengths 1.611(12)1.650(13) A
In relation to the X-ray crystallography of [PW11 O39 (PhPO)2 ]3- ,
it should be noted that the structure analysis of a similar complex
[SiW11 O39 (PhCH2 PO)2 ]4- with C s symmetry has been carried out
without modelling for 2-fold disorder .3i
For 1, the bond valence sum (BVS) values of the W, P and Si
atoms were calculated on the basis of the observed bond lengths.8
The BVS values of the P atoms and Si atoms suggest that these
values correspond reasonably well to the formal valences, P5+ and
Si4+ , respectively. On the other hand, the BVS values of the W
atoms (6.4506.738 and 6.3606.793) were somewhat larger than
+6, indicating the formal valence W6+ , because of the disorder.
Colorless, clear, granular crystals of BuN-3a were obtained by
slow evaporation of a mixed CH3 CNHCl-acidic aqueous medium
containing a 1 : 1 molar ratio of BuN-2 and an SCA at room
temperature. Colorless, clear, granular crystals of BuN-3b were
obtained by slow evaporation of a CH3 CN solution containing
the powder sample, which was prepared by a direct 1 : 4 molarratio reaction of a tri-lacunary Keggin POM and an SCA. Both
crystals belong to the cubic Pa-3 space group and had the same
molecular structures.
The crystals of BuN-3a and BuN-3b used for X-ray crystallography contained a discrete polyoxoanion, three tetrabutylammonium cations, and three solvated CH3 CN molecules, although
1246 | Dalton Trans., 2011, 40, 12431253

Fig.
2 (a)
Molecular
structure
of
the
polyoxoanion
[a-PW11 O39 {(HS(CH2 )3 Si)2 O}]3- (1) in EtN-1, (b) its polyhedral
representation, and (c) the partial structure around the siloxane bond. In
(b), 11 WO6 octahedra are shown in gray, the one central PO4 group is
shown in yellow and the organic groups through the siloxane bond are
shown as Si (light blue), O (red), C (brown) and S (green) atoms.

the CH3 CN molecules were not detected by elemental analysis

and TG/DTA (see Experimental section). In both crystals, all
three Bu4 N cations were assigned. The composition and formula
of BuN-3a and BuN-3b were based on elemental analysis and
TG/DTA. The crystal data of 3a are presented in the Experimental
section. The molecular structure of 3a, its polyhedral representation, and the partial structure around the siloxane bond are shown
) and angles ( ) around the
in Fig. 3a3c. Selected bond lengths (A
siloxane bond in 3a are given in Table 2, while other bond lengths
) and angles ( ) [range] for 3a (Table S2) are deposited in the
(A
ESI.
The asymmetric unit contained one tetrabutylammonium
cation and one third of the anion located at the C 3 axis if the
C 3 axis is that going through O(3), P(1), Si(2), and C(4). A
disorder treatment was introduced for the fourth organic group
containing C5, C6 and S2 atoms. The overall molecular structure
of the 1 : 4 complex anion, 3 (Fig. 3a), is similar to those of
other derivatives of the [a-A-PW9 O34 (RSiO)3 (RSi)]3- 3e,g,h and
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) and angles ( ) around the siloxane
Table 2 Selected bond lengths (A
bond in 3a

Bond lengths/A
Si(1)O(11)i
Si(1)O(12)
Si(1)O(13)
Si(1)C(1)
C(1)C(2)
C(2)C(3)
C(3)S(1)

1.643(4)
1.637(4)
1.607(4)
1.855(5)
1.537(7)
1.520(8)
1.814(7)

Si(2)O(13)
Si(2)C(4)
C(4)C(5)
C(5)C(6)
C(6)S(2)

1.596(4)
1.839(13)
1.25(2)
1.56(2)
1.79(3)

107.1(2)
111.3(2)
111.1(2)
110.7(2)
108.6(2)
108.0(2)
111.8(4)
113.7(5)
114.3(4)
175.1(3)

O(13)Si(2)O(13)i
O(13)Si(2)C(4)
Si(2)C(4)C(5)
C(4)C(5)C(6)
C(5)C(6)S(2)

109.61(17)
109.33(17)
136.0(10)
122.2(18)
115.9(18)

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Bond angles/
O(11)i Si(1)O(12)
O(11)i Si(1)O(13)
O(11)i Si(1)C(1)
O(12)Si(1)O(13)
O(12)Si(1)C(1)
O(13)Si(1)C(1)
Si(1)C(1)C(2)
C(1)C(2)C(3)
C(2)C(3)S(1)
Si(1)O(13)Si(2)

Symmetry operations: i = x-1/2, -y+3/2, -z+1.

Fig.
3 (a)
Molecular
structure
of
the
polyoxoanion
[A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)]3- (3) in BuN-3a, (b) its
polyhedral representation, and (c) the partial structure around the
siloxane bonds. In (b), 9 WO6 octahedra are shown in gray, the one central
PO4 group is shown in yellow and the organic groups through the siloxane
bonds are shown as Si (light blue), O (red), C (brown) and S (green) atoms.

[PW9 O34 (t BuSiO)3 Ge(CH2 )2 CO2 H]3- type.3j The three organosilyl
groups directly supported on the tri-lacunary site can be
This journal is The Royal Society of Chemistry 2011

treated as equivalent groups based on C 3 symmetry, but the

fourth organosilyl group introduced through the siloxane bond
has an asymmetric nature. Thus, the fact that the overall
POM molecule of 3 does not possess any symmetric elements
results in it having C 1 symmetry. The bond lengths and
,
angles of the Si(2)O(13)Si(1) bond [1.596(4)1.607(4) A
175.1(3) ], the angle of the O(13)Si(2)O(13)i bond [109.61(17) ]
and the lengths of the six SiO bonds [Si(1)O(11),i Si(1)
] coordinated to the six terminal
O(12); 1.637(4)1.643(4) A
oxygen atoms in the tri-lacunary site in 3a can be compared
with those of the previously reported related complexes,
i.e., [PW9 O34 (t BuSiO)3 (SiCH2 -CH CH2 )]3- (SiOSi bond
, 173.7 ]),3e [a-A-PW9 O34 (C2 H3 SiO)3 (C2 H3 Si)]3[1.591.65 A
, 175.7178.6 ], the six SiO
(SiOSi bond [1.5061.681 A
3g
]),
[a-A-PW9 O34 (CH3 SiO)3 (CH3 Si)]3bonds [1.6101.641 A
, 173.2176.4 ], the six SiO bonds
(SiOSi bond [1.581.62 A
3g

[1.621.674 A]), [a-A-PW9 O34 (C2 H5 SiO)3 (C2 H5 Si)]3- (SiOSi

, 176.2178.0 ], and the six SiO bonds
bond [1.581.64 A
3h
] is

[1.5931.683 A]). The Ge(1)O(13) length [1.822(14) A

] in
consistently longer than the Si(1)O(13) length [1.558(15) A
[PW9 O34 (t BuSiO)3 Ge(CH2 )2 CO2 H]3- .3j
For 3a, the bond valence sum (BVS) values of the W, P, Si
and O atoms were calculated on the basis of the observed bond
lengths.8 The BVS values of the W atoms were in the range of
6.0706.176 (average 6.126), that of the P atom was 4.976, those
of the Si atoms were in the range of 4.2034.537 (average 4.287),
and those of the O atoms were in the range of 1.7592.219 (average
1.969), suggesting that these values correspond reasonably well to
the formal valences, W6+ , P5+ , Si4+ and O2- , respectively. The BVS
values of the O atoms indicate that all O atoms are unprotonated.
Solid-state and solution NMR
Solid-state (31 P and 29 Si) CPMAS NMR. Solid-state 31 P CPMAS
NMR spectra (Fig. 4) showed a single peak at -13.08 ppm for the
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Fig. 4 Solid-state 31 P CPMAS NMR spectra of (a) (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] EtN-1, (b) (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2, and (c) (Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3a.

Fig. 5 Solid-state 29 Si CPMAS NMR spectra of (a) (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] EtN-1, (b) (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2, and (c) (Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] BuN-3a.

crystalline sample of EtN-1, a broadened peak with a shoulder at

-16.88 ppm for BuN-2 and a single peak at -17.37 ppm for the
crystalline sample of BuN-3. The solid-state 29 Si CPMAS NMR
spectrum (Fig. 5) of the crystalline sample of EtN-1 showed one
resonance at -48.67 ppm. This signal was somewhat shifted to a
lower eld, compared with that of the 1 : 2 complex of the Dawson
analog, [a2 -P2 W17 O61 {(HS(CH2 )3 Si)2 O}]6- , at -50.04 ppm.4b The
solid-state 29 Si CPMAS NMR spectrum (Fig. 5) of BuN-2 showed
a single peak with a shoulder at -44.37 ppm, while that of BuN-3
showed two resonances at -58.26 and -80.56 ppm, which were
assigned to the three Si atoms (Sia ) positioned within the trilacunary site and the fourth Si atom (Sib ) linked through siloxane
bonds to the three Sia atoms, respectively. The solid-state (31 P and
29
Si) NMR spectra of EtN-1 and BuN-3 are compatible with their
solid-state molecular structures revealed by X-ray crystallography.
The solid-state NMR spectra also showed that BuN-2 with silanol
bonds and BuN-3 with siloxane bonds were different species.
Solution (31 P and 29 Si) NMR. Solution 31 P NMR spectra
measured in CD3 CN for the crystalline sample (Fig. 6a) and
the powder sample of EtN-1 showed one resonance at -12.61
and -12.53 ppm, respectively, which was shifted to a higher eld
than that of the mono-lacunary Keggin species, at -10.77 ppm in
D2 O. These 31 P NMR spectra of EtN-1 show that the crystalline
sample is representative of the bulk powder sample, and that
the organosilyl groups supported on the mono-lacunary site are
maintained in solution. Solution 31 P NMR spectra measured in
CD3 CN for BuN-3 showed a single peak at -16.92 ppm, which
was shifted to a higher eld than those of BuN-2, by about 1 ppm.
Solution 29 Si NMR spectra measured in CD3 CN for the Bu4 N
salt of 1, which was separately prepared (see Experimental

section), showed a single peak at -51.17 ppm. Thus, the two Si

atoms supported on the mono-lacunary site behave equivalently
due to the motion in solution, resulting in the approximate
C s symmetry of the whole polyoxoanion. This resonance was
shifted to a higher eld than that of the free SCA in CD3 CN,
at -42.06 ppm. Solution 29 Si NMR spectra measured in DMSOd 6 for BuN-3 showed two resonances: -59.7 ppm due to three
Sia atoms, and -80.17 ppm due to one Sib atom. These signals
correspond to those of the solid-state 29 Si CPMAS NMR, and
therefore show that the solid-state molecular structure revealed by
X-ray crystallography is maintained in solution. The two siloxanebonding polyoxoanions, 1 and 3, showed signicantly different 29 Si
NMR chemical shifts.
On the other hand, solution 31 P NMR spectra measured in
CD3 CN (Fig. 6, inset) for BuN-2 showed two very close resonances
consisting of the main peak at -15.88 ppm and the minor peak
at -15.83 ppm (Dd(P) 0.05 ppm), which are probably due to the
different congurations/orientations of the OH groups around
the Si atoms. There are at least four isomers based on the
orientation of three OH groups; (i) all three OH groups are
arranged inside, (ii) two of the three groups are arranged inside,
(iii) one of the three groups is arranged inside, and (iv) all OH
groups are arranged outside. However, at present, the two 31 P
NMR resonances are not assigned. Correspondingly, solution
29
Si NMR spectra measured in CD3 CN for BuN-2 showed two
resonances consisting of the main peak at -44.47 ppm and the
minor peak at -42.16 ppm (Dd(Si) 2.3 ppm). The origin of the two
31
P NMR resonances in solution should be the same as that of
the two 29 Si NMR resonances in solution. The relative intensities
of these two resonances depended signicantly upon the alcoholic

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Fig. 6 31 P NMR spectra in CD3 CN of (a) (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] EtN-1 as the crystalline sample, (b) (Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] BuN-2, together with the inset showing two very close resonances, and (c) (Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)]
BuN-3a.

solvents, such as MeOH, EtOH, propan-1-ol, and propan-2-ol,

used for reprecipitation. For example, the two relative intensities
(main and minor signals) of the sample obtained with MeOH
as the reprecipitating solvent were inverse to those of the sample
obtained with EtOH. The relative intensities of the two resonances
probably result from the interaction of the alcoholic solvents
with the OH groups of BuN-2, because the reaction solution
containing the 1 : 3 complex before reprecipitation showed a single
31
P NMR peak at -16.13 ppm. The chemical shifts of the solution
29
Si NMR of BuN-2 correspond to those of the solid-state 29 Si
CPMAS NMR, indicating that the 1 : 3 silanol bonding complex
structure is maintained in solution.
In only one example of the structurally determined 1 : 3 silanol
bonding complex, [a-A-PW9 O34 (t BuSiOH)3 ]3- with the bulky tertBu groups,3f is only one isomer (with reference to the orientation
of the silanol groups) present. In this case, all the OH groups
are arranged inside, resulting in a single peak each of solution
29
Si NMR spectra at -46.42 ppm and the 31 P NMR spectra in
DMF/DMSO-d 6 , at -15.9 ppm.
Solution (1 H and 13 C) NMR. 1 H and 13 C NMR spectra measured
in CD3 CN for EtN-1 showed 1 H NMR signals due to the terminal
SH groups at 1.631.67 ppm and 1 H and 13 C NMR signals due to
two organic chains connected through the siloxane bond. 1 H and
13
C NMR spectra measured in CD3 CN for BuN-2 showed broad
This journal is The Royal Society of Chemistry 2011

H NMR signals due to the SiOH (silanol) groups centered at

5.10 ppm, in addition to 1 H and 13 C NMR signals due to the
organic chains corresponding to the 1 : 3 complex structure. These
spectra also indicate that BuN-2 in solution is the 1 : 3 complex
based on the silanol bonds, but not the siloxane bonding complex.
1
H and 13 C NMR spectra measured in CD3 CN for BuN-3 showed
that the silanol groups of 2 disappeared and that the 3 : 1 intensity
ratio of the organic groups on the three Sia atoms and on the one Sib
atom is maintained in solution. These results are also compatible
with the solid-state siloxane-bonding molecular structure of
BuN-3.

Conclusion
Three novel Keggin POM-based, inorganicorganic, hybrid compounds, EtN-1, BuN-2 and BuN-3, were synthesized and unequivocally characterized. In the 1 : 2 complex (EtN-1), two organic
groups connected through a siloxane bond were grafted on a
mono-lacunary site of a Keggin POM, whereas in the 1 : 4 complex
(BuN-3) four organic groups connected through siloxane bonds
were grafted on a tri-lacunary site of a Keggin POM. In the 1 : 3
complex (BuN-2), three organic groups were grafted in the form
of silanol (SiOH), but not through a siloxane bond, on a trilacunary site. The 1 : 4 complex (BuN-3a) was synthesized by a
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1 : 1 molar-ratio reaction of the 1 : 3 complex (BuN-2) with an SCA

and, also, (BuN-3b) by a direct 1 : 4 molar-ratio reaction of a trilacunary Keggin POM with an SCA. Probably, the 1 : 3 complex
(BuN-2) is an intermediate in the formation of the 1 : 4 complex
(BuN-3). The 1 : 3 complex with both terminal thiol groups and
silanol groups also acts as a building block for the formation of
novel hybrid compounds and transition metal cluster complexes.
This example of synthetic chemistry will be reported in due course.
From the viewpoint of the hostguest relationship between the
incorporated Si atom and the lacunary site of the POM, the 1 : 2
complex (EtN-1) is conveniently classied as a one-host/two-guest
compound, the 1 : 3 complex (BuN-2) as a three-host/three-guest
compound, and the 1 : 4 complex (BuN-3) as a three-host/fourguest compound, although the relationship is not based on noncovalent interaction.11

Experimental
Materials
The following were used as received: EtOH, MeOH, CH3 CN,
Et2 O, Et4 NBr, Bu4 NBr, 6 M and 1 M aqueous HCl solutions (quantitative analysis grade, all from Wako); silane
coupling agents (SCAs), i.e., 3-mercaptopropyltrimethoxysilane
(HS(CH2 )3 Si(OMe)3 ) (Chisso); CD3 CN, DMSO-d 6 (Isotec).
One POM precursor, the tri-lacunary Keggin POM, Na9 [APW9 O34 ]15H2 O,9 was prepared according to the literature and
identied by FTIR, TG/DTA and 31 P NMR. Another POM
precursor, K7 [a-PW11 O39 ]13H2 O, was prepared and characterized
by FTIR, TG/DTA and 31 P NMR (see ESI).
Instrumentation and analytical procedures
Elemental analyses were carried out with a PerkinElmer 2400
CHNS Elemental Analyzer II (Kanagawa University). Complete
elemental analyses were carried out by Mikroanalytisches Labor
Pasher (Remagen, Germany). The samples were dried at room
temperature under 10-3 10-4 torr overnight before analysis. Infrared spectra were recorded on a Jasco 4100 FT-IR spectrometer
on KBr disks at room temperature. Thermogravimetric (TG) and
differential thermal analyses (DTA) were done using a Rigaku
Thermo Plus 2 series TG/DTA TG 8120 instrument. TG/DTA
measurements were run in air with a temperature ramp of 4 C
per min between 20 and 500 C and the sample was kept at 500 C
for one hour.
1
H (399.65 MHz), 13 C{1 H} (100.40 MHz), 31 P (161.70 MHz)
and 29 Si (79.30 MHz) NMR spectra in CD3 CN and DMSO-d 6
were recorded in 5 mm outer diameter tubes on a JEOL JNM-EX
400 FTNMR spectrometer, with a JEOL EX-400 NMR dataprocessing system. 1 H (500.16 MHz), 13 C{1 H} (125.78 MHz), 31 P
(202.47 MHz), and 29 Si (99.368 MHz) NMR spectra in CD3 CN
and DMSO-d 6 were recorded in 5 mm outer diameter tubes on
a JEOL ECP 500 FTNMR spectrometer using a JEOL ECP500 NMR data-processing system. 1 H, 13 C{1 H} and 29 Si NMR
spectra were measured in CD3 CN and DMSO-d 6 referenced to an
internal standard of tetramethylsilane SiMe4 . 31 P NMR spectra
were referenced to an external standard of 25% H3 PO4 in H2 O
in a sealed capillary. 31 P NMR data with the usual 85% H3 PO4
reference are shifted to +0.544 ppm from our data. Solid-state 31 P
1250 | Dalton Trans., 2011, 40, 12431253

(121.00 MHz) and 29 Si (59.71 MHz) CPMAS NMR spectra were

recorded in 6 mm outer diameter rotors on a JEOL JNM-ECP
300 FTNMR spectrometer with a JEOL ECP-300 NMR dataprocessing system. These spectra were referenced to an external
standard, (NH4 )2 HPO4 and polydimethylsilane. Chemical shifts
are reported as negative for resonances upeld of (NH4 )2 HPO4 (d
1.60) and polydimethylsilane (d -34.0).
Synthesis
(Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] (EtN-1). As an SCA,
HS(CH2 )3 Si(OMe)3 (630 mL (3.4 mmol)) was added to 300 mL of
a solvent mixture of CH3 CNH2 O (200/100 v/v) and solid K7 [aPW11 O39 ]13H2 O (5.4 g (1.7 mmol)) was added to the solution.
The dispersed solution was adjusted to pH 0.5 with a 6 M aqueous
HCl solution. After stirring for 30 min at room temperature, the
resulting pale yellow clear solution was concentrated to ca. 100 mL
in volume with a rotary evaporator at 30 C. Et4 NBr (5.5 g (26
mmol)) was then added to it. After stirring for 30 min at room
temperature, a yellowwhite powder formed, was collected on a
membrane lter (JG 0.2 mm), washed with H2 O (50 mL, 3 times),
EtOH (30 mL, 3 times) and Et2 O (30 mL, 3 times), and dried
in vacuo for 2 h. At this stage, a yellowwhite powder was obtained
in a yield of 5.26 g.
Crystallization. The yellowwhite powder (2.0 g) was added
to 64 mL of acetonitrile and then 20 mL of a 1 M aqueous
HCl solution was added dropwise, followed by stirring for
30 min at room temperature. The resulting colorless solution
was ltered with a folded lter paper (Whatman #2), followed
by slow evaporation at room temperature in the dark. After a
few days, yellow rod crystals formed. The crystals, collected on a
membrane lter (JG 0.2 mm), washed with H2 O (30 mL, 3 times),
EtOH (30 mL, 3 times) and Et2 O (30 mL, 3 times), and dried
in vacuo for 2 h, were obtained in 54.1% yield (1.07 g scale).
The crystals obtained were soluble in hot acetonitrile, dimethyl
sulfoxide, sparingly soluble in acetonitrile, and insoluble in water,
methanol, ethanol and diethyl ether. {Found (repeat analysis of
an independent preparation): C, 10.95 (10.99); H, 2.28 (2.04);
N, 1.37 (1.29); O, 19.5; Si, 1.65; P, 0.92; S, 1.87; W, 61.3%,
total 99.84%. Calc. for (Et4 N)3 [a-PW11 O39 {(HS(CH2 )3 Si)2 O}] or
C30 H74 N3 O40 Si2 P1 S2 W11 : C, 10.95; H, 2.27; N, 1.28; O, 19.45; Si,
1.71; P, 0.94; S, 1.95; W; 61.46%}. Weight loss during the course
of drying at room temperature at 10-3 10-4 torr overnight before
analysis was negligible. TG/DTA under atmospheric conditions:
no weight loss was observed before decomposition. A weight loss
of 14.71% was observed at under 502.0 C with exothermic points
at 330.1 and 407.3 C based on the decomposition of Et4 N+ cations
and organic groups. FTIR (KBr): 2573 m [SH], 1483 s, 1460 m,
1439 m, 1392 m, 1365 m, 1304 m, 1254 m, 1182 m, 1173 m,
1111 s [SiOSi], 1066 s, 1055 s, 1034 s, 997 s, 964 vs, 899 m,
868 vs, 822 vs, 785 vs, 710 s, 598 w, 584 w, 523 m, 507 w, 469
w, 453 w, 422 w cm-1 . Solid-state 31 P CPMAS NMR: d -13.08.
Solid-state 29 Si CPMAS NMR: d -48.67. 31 P NMR (21.9 C,
CD3 CN): d -12.61. 29 Si NMR of a separately prepared Bu4 Ncation compound (18.5 C, CD3 CN): d -51.17. [Note: Since the
Et4 N-cation compound did not have enough solubility in CD3 CN,
the much more soluble Bu4 N-cation compound was independently
prepared.] 1 H NMR (22.2 C, CD3 CN): d 0.890.93 (SiCH 2 ),
1.631.67 (SH), 1.841.89 (CH 2 ), 2.602.69 (CH 2 S),
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1.251.28 and 3.203.25 (Et4 N). 13 C NMR (25.6 C, CD3 CN): d

11.92 (SiCH2 ), 27.78 (CH2 S), 28.57 (CH2 ), 7.80 and 53.25
(Et4 N).
(BuN-2). Bu4 NBr
(Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ]
(5.5 g (17.1 mmol)) was dissolved in 60 mL of CH3 CN. To it
HS(CH2 )3 Si(OMe)3 (1032 mL (5.55 mmol)) and solid Na9 [APW9 O34 ]15H2 O (5.0 g (1.85 mmol)) were added. To the solution
14 mL of a 1 M aqueous HCl solution was added dropwise
. By allowing the solution to stand for a few minutes, the
resulting colorless solution separated into two layers, i.e., the
upper organic layer and the lower aqueous layer. The aqueous
layer was removed, the organic layer was ltered with a folded
lter paper (Whatman #5), and the ltrate was directly dropped
into 1000 mL of methanol in an ice bath. After stirring for
30 min in the ice bath, a white powder formed, was collected on
a membrane lter (JG 0.2 mm), washed with MeOH (30 mL,
3 times) then Et2 O (30 mL, 3 times), and dried in vacuo for 2 h.
The white powder changed to pink powder during the course
of drying in vacuo. At this stage, the pink powder was obtained
in 41.5% yield (2.55 g scale). The powder obtained was soluble
in acetonitrile, dimethyl sulfoxide and acetone, but insoluble
in water, methanol, ethanol, dichloromethane, chloroform and
diethyl ether. {Found: C, 20.17; H, 3.77; N, 1.22%. Calc. for
(Bu4 N)3 [A-PW9 O34 (HS(CH2 )3 SiOH)3 ] or C57 H132 N3 O37 Si3 P1 S3 W9 :
C, 20.64; H, 4.01; N, 1.27%}. TG/DTA under atmospheric
conditions: no weight loss was observed before decomposition
and a weight loss of 26.77% was observed at under 501.2 C with
an exothermic point at 364.0 C. FTIR (KBr): 2567m[SH], 1633
m, 1483 m, 1469 m, 1383 m, 1344 m, 1308 m, 1257 m, 1151 m,
1099 vs, 1036 m, 1005 m, 966 vs, 943 vs, 868 vs, 841 vs, 731 s, 600
w, 579 m, 525 m, 511 m, 488 w, 478 w, 461 w, 444 w, 426 w cm-1 .
Solid-state 31 P NMR: d -16.88. Solid-state 29 Si CPMAS NMR: d
-44.37. 31 P NMR (22.4 C, CD3 CN): d -15.83 (minor), -15.88
(main). 29 Si NMR (23.3 C, CD3 CN): d -42.16 (minor), -44.47
(main). 1 H NMR (22.6 C, CD3 CN): d 0.710.75 (SiCH 2 ),
1.701.76 (CH 2 ), 2.542.59 (CH 2 S), 5.10 (SiOH, br), 1.00,
1.41, 1.65 and 3.15 (Bu4 N). 13 C NMR (23.7 C, CD3 CN): d 13.37
(SiCH2 ), 27.96 (CH2 S), 29.01 (-CH2 -), 14.00, 20.43, 24.44
and 59.37 (Bu4 N).
[Note: The reprecipitating solvents, such as MeOH, EtOH,
propan-1-ol, and propan-2-ol signicantly inuenced the relative
intensities of the two resonances (main and minor peaks) in the
solution (31 P and 29 Si) NMR spectra of the isolated samples.]
(Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] (BuN-3a)
Preparation by a reaction of BuN-2 with HS(CH2 )3 Si(OMe)3 . BuN2 (0.3 g (0.09 mmol)) and HS(CH2 )3 Si(OMe)3 (16.7 mL (0.09
mmol)) were added to 10 mL of CH3 CN. To the solution was added
2 mL of a 1 M aqueous HCl solution. After stirring overnight at
room temperature in a sealed system, the resulting colorless clear
solution was ltered with a folded lter paper (Whatman #5),
followed by slow evaporation at room temperature in the dark.
The next day, colorless clear granular crystals formed. The crystals,
collected on a membrane lter (JG 0.2 mm), washed with MeOH
(30 mL, 3 times) then Et2 O (30 mL, 3 times), and dried in vacuo
for 2 h, were obtained in 45.5% yield (0.14 g scale). The crystals
obtained were soluble in hot acetonitrile, dimethyl sulfoxide,
sparingly soluble in acetonitrile, and insoluble in water, methanol,
This journal is The Royal Society of Chemistry 2011

ethanol and diethyl ether. {Found: C, 21.20; H, 3.94; N, 1.42%.

Calc. for (Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] or
C60 H136 N3 O37 Si4 P1 S4 W9 : C, 21.09; H, 4.01; N, 1.23%}. TG/DTA
under atmospheric conditions: no weight loss was observed before
decomposition and a weight loss of 28.46% was observed at below
501.1 C with an exothermic point at 369.2 C. FTIR (KBr): 2565
m [SH], 1485 s, 1381 m, 1340 m, 1306 m, 1257 m, 1238 m, 1157 s,
1122 vs [SiOSi], 1039 m, 1001 m, 976 vs, 957 vs, 945 vs, 866 vs,
814 vs, 727 vs, 600 w, 580 w, 532 m, 509 m, 480 w, 461 w cm-1 . Solidstate 31 P CPMAS NMR: d 17.37. Solid-state 29 Si CPMAS NMR:
d -58.26 (Sia ), -80.56 (Sib ). 31 P NMR (23.0 C, CD3 CN): d -16.92.
29
Si NMR (23.0 C, DMSO-d 6 ): d -59.17 (Sia ), -80.71 (Sib ).
1
H NMR (23.4 C, CD3 CN): d 0.670.71 (Sib CH 2 ), 0.730.75
(Sia CH 2 ), 1.681.74 (Sia CH2 CH 2 and Sib CH2 CH 2 ), 2.47
2.51 (Sib CH2 CH2 CH 2 ), 2.522.59 (Sia CH2 CH2 CH 2 ), 0.99,
1.40, 1.64 and 3.14 (Bu4 N). 13 C NMR (23.6 C, DMSO-d 6 ): d
12.75 (Sib CH2 ), 12.81 (Sia CH2 ), 26.83 (Sia CH2 CH2 CH2 ),
27.02 (Sib CH2 CH2 CH2 ), 27.66 (Sia CH2 CH2 ), 27.82 (Sib CH2
CH2 ), 13.47, 19.19, 23.07 and 57.56 (Bu4 N). [Note: The Sia atoms
are positioned within the tri-lacunary site and the Sib atom is
linked through siloxane bonds to the three Sia atoms.]
(Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] (BuN-3b)
Preparation by a direct 1 : 4 molar-ratio reaction of tri-lacunary Keggin POM with HS(CH2 )3 Si(OMe)3 . HS(CH2 )3 Si(OMe)3 (744 mL
(4.0 mmol)) was added to 200 mL of a solvent mixture of CH3 CN
H2 O (150/50 v/v). The solution was acidied with 5 mL of a
6 M aqueous HCl solution. To it was slowly added the precursor
Na9 [A-PW9 O34 ]15H2 O (2.7 g (1.0 mmol)) with a small portion,
because the precursor is unstable in water. The resulting colorless
clear solution was concentrated to ca. 60 mL in volume with a
water bath at 80 C. To it was added Bu4 NBr (3.0 g (9.3 mmol)).
After stirring for 30 min at room temperature, a white powder
formed, was collected on a membrane lter (JG 0.2 mm), washed
with H2 O (30 mL, 3 times), EtOH (30 mL, 3 times) and Et2 O
(30 mL, 3 times), and dried in vacuo for 2 h. At this stage, a crude
product was obtained in a yield of 3.29 g. Using this product, (1)
crystallization was carried out and (2) purication to yield pure
powder was also performed. Both compounds obtained in (1) and
(2) were pure and of the same composition.
(1) Crystallization. The crude product (3.16 g) was dissolved in
30 mL of CH3 CN in a water bath at 80 C. The hot, colorless,
clear solution was immediately ltered with a folded lter paper
(Whatman #5), followed by slow evaporation at room temperature
in the dark. After a few hours, colorless, clear, granular crystals
formed. The crystals, collected on a membrane lter (JG 0.2 mm),
washed with EtOH (30 mL, 3 times) then Et2 O (30 mL, 3
times), and dried in vacuo for 2 h, were obtained in 49.7%
yield (1.70 g scale). {Found (repeat analysis of an independent
preparation): C, 20.99 (21.11); H, 4.16 (3.80); N, 1.26 (1.23);
O, 15.5; Si, 3.18; P, 0.89; S, 3.59; W, 48.3%, total 97.87%.
Calc. for (Bu4 N)3 [A-a-PW9 O34 (HS(CH2 )3 SiO)3 (Si(CH2 )3 SH)] or
C60 H136 N3 O37 Si4 P1 S4 W9 : C, 21.09; H, 4.01; N, 1.23; O, 17.32; Si,
3.29; P, 0.91; S, 3.75; W; 48.41}. Weight loss during the course
of drying at room temperature at 10-3 10-4 torr overnight before
analysis was negligible. TG/DTA under atmospheric conditions:
no weight loss was observed before decomposition and a weight
loss of 29.98% was observed at below 501.1 C with exothermic
Dalton Trans., 2011, 40, 12431253 | 1251

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points at 368.7, 387.2 and 396.1 C. FTIR (KBr): 2566 m [SH],

1485 m, 1381 m, 1341 m, 1306 m, 1257 m, 1240 m, 1158 m,
1121 vs [SiOSi], 1038 m, 1001 m, 975 vs, 957 vs, 945 vs, 866
vs, 814 vs, 727 vs, 600 w, 580 w, 533 m, 508 m, 484 w, 474
w cm-1 . 31 P NMR (22.7 C, CD3 CN): d -16.93. 1 H NMR (22.8 C,
CD3 CN): d 0.680.71 (Sib CH 2 ), 0.720.75 (Sia CH 2 ), 1.68
1.74 (Sia CH2 CH 2 and Sib CH2 CH 2 ), 2.472.52 (Sib CH2 CH2
CH 2 ), 2.532.58 (Sia CH2 CH2 CH 2 ), 0.98, 1.39, 1.63 and 3.12
(Bu4 N). 13 C NMR (25.1 C, DMSO-d 6 ): d 12.68 (Sib CH2 ),
12.74 (Sia CH2 ), 26.76 (Sia CH2 CH2 CH2 ), 26.94 (Sib CH2 CH2
CH2 ), 27.64 (Sia CH2 CH2 ), 27.78 (Sib CH2 CH2 ), 13.42, 19.12,
22.98 and 57.47 (Bu4 N).
(2) Purication by washing with acetonitrile at room temperature.
The crude product (3.21 g) was suspended in 16 mL of CH3 CN at
room temperature. After stirring for 30 min at room temperature,
an undissolved powder, which was collected on a membrane lter
(JG 0.2 mm), washed with EtOH (30 mL, 3 times) and Et2 O (30 mL,
3 times), and dried in vacuo for 2 h, was recovered in 48.8% yield
(1.67 g scale). Solid-state 31 P CPMAS NMR: d -17.12. Solid-state
29
Si CPMAS NMR: d -58.26 (Sia ), -80.56 (Sib ).
Both compounds in (1) and (2) were soluble in hot acetonitrile,
dimethyl sulfoxide, sparingly soluble in acetonitrile, and insoluble
in water, methanol, ethanol and diethyl ether.
X-Ray crystallography
Crystals of compounds EtN-1 and BuN-3a were covered with
parafn oil and Paratone-N (liquid parafn), respectively, to
prevent their degradation. The crystal sizes were 0.16 0.08
0.02 mm, and 0.20 0.14 0.06 mm, respectively. Data collection
was done with a Bruker SMART APEX CCD diffractometer at
90 K in the range of 1.27 < q < 23.33 (EtN-1) and 1.28 <
q < 28.30 (BuN-3a). The smaller angles for EtN-1 come from the
smaller crystals. The intensity data were automatically corrected
for Lorentz and polarization effects during integration. The structure was obtained by direct methods (SHELXS-97),10a followed by
a difference Fourier calculation, and rened by a full-matrix, leastsquares procedure on F 2 (program SHELXL-97).10b Absorption
correction was performed with SADABS (empirical absorption
correction).10c The composition and formula of the POM were
determined by complete elemental analysis and TG/DTA analysis.
Crystal data for EtN-1. C30 H74 N3 O40 P1 S2 Si2 W11 , M = 3290.54,
Monoclinic, space group P2(1)/n, a = 12.856(2), b = 21.702(4), c =
, b = 101.684(4), V = 6655(2) A
3 , Z = 4, Dc = 3.284
24.359(5) A
-3
-1
Mg m , m(Mo-Ka) = 19.139 mm . R1 = 0.0666, wR2 = 0.1225
(for all data). Rint = 0.0558, R1 = 0.0530, wR2 = 0.1146, GOF =
1.046 (45132 total reections, 9618 unique reections where I >
2s (I)). As to composition, 3 Et4 N cations and polyoxoanion 1
consisting of 11 tungsten atoms, one phosphorus atom, 40 oxygen
atoms, 2 silicon atoms, 6 carbon atoms, and 2 sulfur atoms per
formula unit were identied. A 2-fold-disordered structure was
observed for this POM.3c Hydrogen atoms were rened only for
the organosilyl groups. CCDC number 790105.
Crystal data for BuN-3a. C66 H145 N6 O37 P1 S4 Si4 W9 , M =
3541.10, Cubic, space group Pa-3, a = 27.5792(9), V = 20977.1(12)
3 , Z = 8, Dc = 2.243 Mg m-3 , m(Mo-Ka) = 10.043 mm-1 . R1 =
A
0.0331, wR2 = 0.0735 (for all data). Rint = 0.0587, R1 = 0.0277,
wR2 = 0.0701, GOF = 1.177 (271384 total reections, 8715 unique
1252 | Dalton Trans., 2011, 40, 12431253

reections where I > 2s (I)). As to composition, 3 Bu4 N cations,

3 CH3 CN molecules and polyoxoanion 3a consisting of 9 tungsten
atoms, one phosphorus atom, 37 oxygen atoms, 4 silicon atoms,
12 carbon atoms, and 4 sulfur atoms per formula unit were
identied. A disorder-free polyoxoanion structure was identied.
Two terminal carbon atoms connected through an SiOSi
bond and one sulfur atom of the grafted organic groups were
disordered. Hydrogen atoms were rened for the organosilyl
groups, except for the disordered groups. In the crystals, three
solvated CH3 CN molecules were identied, although they were
not detected by elemental analysis and TG/DTA. To maintain the
crystal structure, three CH3 CN molecules are probably required,
but they are readily lost at room temperature. In fact, when the
crystals were handled under air at room temperature, the crystals
soon degraded by loss of the CH3 CN molecules. CCDC number
790104.

Acknowledgements
This work was supported by a Grant-in-Aid for Scientic Research
(C), No. 22550065, from the Ministry of Education, Culture,
Sports, Science and Technology, Japan.

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