L. de Qumica Inorganica I, No.

14, 2016-10

Polioxometalatos
Angewandte

Polyoxometalate1,2
Juan
Barbosa Structures
*, Alejandro Camacho1,3 **

Chemie

P
olyoxometalates (POMs) are a subset of metal oxides that represent
Abstract

From the Contents

aDiez
diverse
rangeson
of molecular
clusters
an almost
unmatched
range
reacciones
llevadas a cabo
para with
estudiar
polioxometalatos
de molibdeno
y tungsteno. La formacion de los
1. The Growth in Polyoxometalate
of
physical
properties
the ability
form
that de
oxidos
metalicos
se da enand
ausencia
de calor.toSe
usa dynamic
la coloraciostructures
n como indicativo
la formacion del producto. Entre

Chemistry
1737
los
polioxometalatos
de
molibdeno
estudiados,
algunos
presentan
estructuras
de
Keggin
y se destacan el heptamolibdato,
can range in size from the nano- to the micrometer scale. Herein we
y azul dethe
molibdeno.
En los
polioxometalatos
delsynthesis
vanadio setoevidencia
la and
dependencia
del pH, entre los que se destaca
present
very latest
developments
from
structure
2. Classification and Design
la formaci
on de peroxovanadatos el cual posee una geometra trigonal bipiramidal. Principles
1738
function of POMs. We discuss the possibilities of creating highly
Keywords
sophisticated
functional hierarchical systems with multiple, inter3. POM Nanostructures and
Polioxometalatos, oxidos metalicos, compuestos cluster, molibdeno, vanadio
dependent, functionalities along with a critical analysis that allows the
Nanocomposities
1744
1 Departamento de Qu
de los
Andes, Bogot
, Colombia and present a
non-specialist tomica,
learnUniversidad
the salient
features.
Weapropose
2 Departamento de F
sica, Universidad de los Andes, Bogot
a, Colombia
table
of polyoxometalate
blocks. We also highlight 4. Engineering Functionality:
3periodic
Departamento
de Fsica,
Universidad Nacional,building
Bogot
a, Colombia
From Molecules to Materials
1750
some of
the current issues and challenges that need to be addressed to
*Email:
js.barbosa10@uniandes.edu.co
**Email:
a.camacho10@uniandes.edu.co
work towards the design of functional systems based upon POM
5. Catalytic Applications in Green
building blocks and look ahead to possible emerging application areas.
Chemistry and Energy Systems 1752

Introducci
on
1. The
Growth in Polyoxometalate
Chemistry
Los
polioxometalatos
(POMs) son oxidos
de metales con
un estado de agrupacion molecular (molecular clusters)
Polyoxometalate
clusters dos
have
an de
unmatched
de tama
no variable. (POM)
Se distinguen
tipos
polioxrange
of
physical
and
chemical
properties,
acting
as ao set
ometalatos dependiendo de la existencia de una
maof
s
transferable building blocks that can be reliably utilized in the
especies met
alicas interactuando en el cluster. En el
formation of new materials. These key features are being
primer caso se habla de iso-polioxometalatos mientras en
exploited rapidly today after a rise in popularity of POMs,
el segundo se usa hetero-polioxometalatos [6]. Los POMs
which started in the early 1990s as a result of a Review by
mas comunes son[1]los de metales del grupo 6, sin embargo
Pope and Mller in 1991 that foresaw the present explosion.
se los encuentra del grupo 5 en menor proporcion [7].
The vast growth was also well-documented in 1998, when a
La historia
los in
polioxometalatos
enby1826
special
thematicdeissue
Chemical Reviewsempieza
organized
Hill
con
el
fosfomolibdato
de
amonio
((NH
)
PMo
el
3
12 O40
presented the history, developments, and4 application
of) the
[2]
cual
se
obtiene
al
agregar
molibdato
de
amonio
en
exmany areas covered by POM chemistry.
ceso Today,
de acido
fosf
orico [8]. isLaa qu
mica
de este
nuevo
POM
chemistry
key
emerging
area
that
compuesto
fue
estudiada
por
Werner,
quien
trat
o
de expromises to allow the development of sophisticated designer
plicar
su estructura
a partir
su reciente
teoradevelopde los
molecule-based
materials
andde
devices
that exploit
compuestos
de
coordinaci
o
n.
En
la
elucidaci
o
n
trabaments in instrumentation, nanoscale science, and material
jaron
renombrados
qu
micos quienes
con
teoras
fabrication
methods.
However,
despite
alldistintas
the promise,
the
e relentless
hipotesisincrease
trataron
de infructuosamente
la
in the
number of structuresdeterminar
and derivatives
mean that Entre
it can ellos
be difficult
to distinguish
the
estructura.
se destacan
Miolati, between
Pizzighelli,
different cluster
types and
Thehasta
reason
forque
the
Rosenheim,
y Pauling.
Fue subtypes.
u
nicamente
1934
explosion
the number
of structurally
POM
J.F.
Keggininusando
difracci
on de rayoscharacterized
X determin
o la
compoundsdel
is mismo
due to developments
in instrumentation and
estructura
[9].
novel
synthetic
approaches.
In
terms
technique
developPara la mitad del siglo XX cientosofde
compuestos
poment, fast andhab
routine
single
crystal data
collection
has
lioxometalatos
an sido
estudiados.
Sin embargo
poco
the area
accelerate
to the point
the bottle neck
seallowed
saba sobre
sutosntesis,
degradaci
on ethat
interconversi
on.
has moved tofueron
structure
refinement
or tocomo:
crystallization
of new
Inicialmente
usadas
tecnicas
polarograf
a,
compounds
rather
than
the
time
taken
for
data
collection
and
espectrometra, magnetoqumica y ultracentrifugacio
n.
initial structure solution. There are over 500 papers (not
Para
los a
nos 70 la aplicacion de la espectroscopa Raman
including patents) published each year that involve at least
e infraroja permitio avances en la elucidacion estructural
some aspect of POM chemistry, and this number is rapidly
[9].
increasing (Figure 1). In the last few years, a number of
Hoy en da son muy usadas las tecnicas de RMN
Reviews have appeared that address different aspects of
y POM
difracci
on deincluding
monocristal
para la determinaci
on de
science,
new structures,
biomedical applicalas
estructuras.
Estas u
ltimas
han permitido
que en for
la
tions,
catalysis, theoretical
calculations,
and perspectives
new materials.[3, 4] Herein, we will focus on very recent
developments that have enabled new synthetic routes,
analysis, self assembly to nanostructures, design of functional
systems. Of course, the inspiration for much of these concepts
comes from early pioneering work,[1, 2] which demonstrates

actualidad se realicen6. m
as de 500 publicaciones anuales
Summary and Outlook:
con referencia a los polioxometalatos
[6]. the
La Figura 1
Polyoxometalates and
permite ver el rapido Emergence
crecimiento
que
han
tenido1754
los
of New Phenomena
compuestos cluster de oxidos metalicos.

Figura
N
umero ofdepublications
publicaciones
sobre
Figure 1.1.The
number
that involve
thePOMs
study of en
polyoxo-

escala
logar
tmica
entheelyear.
tiempo
metalates
plotted
against
The y [6].
axis is plotted on a
logarithmic scale showing a linear trend.

the Debido
fundamental
al n
uidea
merothat
de
apolyoxometalate-based
tomos presentes en elnanosyscluster,
[3]
tems
with
well-defined
functionality
could be possible.
resulta difcil determinar las estructuras
de los polioxThis reviewEn
aims
be not2 only
a snapshot
of tabla
the recent
ometalatos.
la to
Figura
se muestra
una
que
developments made during the past couple of years in terms
permite clasificar la estructura de los POMs de molibof design, architecture, and application, but also to be
deno, tungsteno, vanadio y niobio, a partir de el n
umero
employed as a guide to understand the many different cluster
de oxgenos y otros ligandos. Existen tres tipos de estructypes and subtypes, and in particular to understand the
tura mayoritarios: Lindqvist, Keggin, y Dawson. Siendo
structural formulae. We place a special emphasis on systems
la segunda la que posee la mayor variedad de compuestos
that show multifunctionality and on how the cluster temde
tungsteno (Figura 3). Existen dos estructuras adiplates, resulting building blocks, sub-structures, and overall

cionales para el molibdeno: la esfera cafe (Brown Sphere)

y la rueda az
ul (Blue Wheel) [6].
[*] Dr. D.-L. Long, Dr. R. Tsunashima, Prof. L. Cronin
WestCHEM, Department of Chemistry
The University of Glasgow
University Avenue, Glasgow G12 8QQ, Scotland (UK)
Fax: (+ 44) 141-330-4888
E-mail: L.Cronin@chem.gla.ac.uk

Angewandte
Polioxometalatos
2/5

Polyoxometalate Structures

984

Chemie

Ch. 22

Vanadium, Niobium and Tantalum

In alkaline solution:
observed data. However, the greater the
complexity of the system, the greater the
Figura
2.
[V04l3- based
H+
Figure
2.
POM
nuclearity
using
a
classification
on[HV04I2building blocks of high-nuclearity clusters (Mo, W, V and Nb POMs).[113] The generic
number of apparently acceptable models
there
will
be,
and
the
greater
the
accu[V207l4HzO
2[HV04I2building blocks (in boxes with solid black lines)
have been
isolated
as stable clusters: W11 isopolyanion, lacunary Keggin (W9X, W10X, W11X),
racy required if the measurements are
H+ 1
[H2V04]lacunary
Dawson
isopolyanions.
These
building blocks can be linked to form higher nuclearity clusters of nuclearity n by
z)P2), and Nb24 [HV04l2to distinguish
reliably (W
and(18
unambiguously
betweenLthem.
linkers
that contain a transition metal ion,
alkyl metals,[V309l3or heteroions.
3H20 Thus (W9)n(Lm) is composed of n W9 building blocks assembled with
3[H2V04]-

Clasificaci
on de
f
ormulas de polioxometalatos conocidos actualmente [6].
+ las
+
+
+
+

+
+
+
+
Estructura de Keggin. Modificado de [10].

1. Metodologa

of general
formula
X[V4012l4are omitted
here). Structural building blocks (in boxes with dashed lines) have not been
4H20
4[H2V04]Of several
the manylinkers
experimental
techniques
which Lm (the heteroatoms
Figura
3.in this field,
have isolated
been used
the but
morecan be considered as building blocks for high-nuclearity POMs. These are: M5 (one-metal lacunary Lindqvist;
as clusters
to date,
In acid solution:
3
important are: pH measurements, cryoscopy, ionlacunary
Dawson), and3[HVl002,]~M(M5) (pentagonal
building blocks; M = Mo, W and Nb). Note: solid and dashed
M = W, V, Nb), W12Pspectroscopy
2 (hexavacant
10[V309]3- + 15H'
exchange and ultraviolethisible
for
+ 6H20
arrows
do not correspond
to synthetic routes.
category are the noble metal POMs, where X = As for the Pd compound, and X = S for
studying
the stoichiometry
of the equilibria,
+H3V04
[HzV04]-In+aH+separate
and the
infrared/Raman
and nmr spectroscopy
Pt compound.
[HVioo2815H+
[H2Vi0028]~for studying the structures of the ions in
H3V04 + H+ e V02' + 2H20
solution, where oxygen-I7 and metal atom
nmr spectroscopy are playing an increasingly
10V02+ + 8 H 2 0
[HzVl0028]~-+ 14H+
Synthetically, the route to produce new POM clusters are
all role.
empirically
based,
an appreciation of
the pHimportant
Probably the best
summaryand
of
our current understanding of the vanadate system
In these equilibria the site of protonation in
often
very simple synthetic manipulations requiring a small
dependent
speciation
of
metalates
can
often
be
the
key
is given by Fig. 22.2. This shows how the
the species [HV04I2-, [H2V04]- etc., is an
existence
of the various
vanadate
species
depends Generally,
oxygen atom (not
a moreused
precise
number of steps, or even just one step (one-pot syntheses;
starting
point
in the
synthesis.
the vanadium);
approaches
on the pH and on the total concentration of
representation would therefore be [VO3(OH)]2-,
Figure 4). The acidification, for example, of a solution of
to produce
POM
based
clusters
are simple,
consisting
of
vanadium.(')
Their occurrence
can be
accounted
[V02(OH)2]etc. However,
the customary
formulation
is retained the
for convenience
(cf.
for by
protonation andan
condensation
equilibria
sodium molybdate will give rise to metal oxide fragments,
acidifying
aqueous
solution
containing
relevant
HNO3, HSO4-, H2SO4, etc.).
such as the following:

Los polioxometalatos tienen propiedades u

nicas, por
lo cual poseen aplicaciones numerosas.
+ Entre
+ ellas se
destacan el dise
no molecular de materiales, nanotecnologa, instrumentaci
on, cat
alisis, aplicaciones medicas,
y fabricacion de materiales [6]. Muchas de estas dependen directamente del pH, en la Figura 4 se muestran
diferentes POMs del vanadio en solucion en funcion del
pH.

molybdate and tungstate oxoanions (vanadates tend to be

synthesized at high pH).[3] POM systems are complex owing
to many thousands of combinatorially possible structure
types, in which each building block can itself adopt a range of
potential isomers.

Leroy (Lee) Cronin graduated in Chemistry

in 1994 from the University of York, and
obtained a DPhil. in bio-inorganic chemistry
in 1997 under the supervision of Prof. P. H.
Walton. After postdoctoral research at Edinburgh University with Neil Robertson and as
Alexander
vonas Humboldt
Figure 22.2 Occurrence
of various vanadate andan
polyvanadate
species
a function of pHResearch
and total concentration

Figuraof4.
Oxidos
y
polioxometalatos
de
vanadio
en
vanadium.
Fellow with Prof. A. Mller at the University
funci
on del pH [7].
of Bielefeld (Germany), he returned to the
UK as a lecturer at the University of Birmingham
in 2000. In
2002 took up apara
Los conceptos anteriores
resultan
importantes
in Glasgow; he wasde
promoted
to
entender la formacion deLectureship
los polioxometalatos
molibReader in 2005, Professor in 2006, and was
deno y vanadio estudiados
en la practica de laboratorio.
appointed to the Gardiner Chair of Chemistry in April 2009. He is a Fellow
of the Royal Society of Edinburgh, Scotlands National Academy of Science
and Letters.

Angew. Chem. Int. Ed. 2010, 49, 1736 1758

En un tubo de ensayo aproximadamente 0.10 g de MoO

son disueltos en 1.0 mL de solucion de NaOH 2.0 mol/L.
Sobre esta se adicionan varias gotas de HCl 2.0 M. Para
las siguientes cinco reacciones se prepara 5.0 mL de una
soluci
on acuosa de molibdato de amonio tetrahidratado.
En un segundo tubo de ensayo se adiciona 1.0 mL de la
solucion anterior y se acidifica con unas gotas de HCl,
finalmente se agrega una perla de zinc. Usando el mismo
volumen de solucion de molibdato de amonio se adicionan
3which
gotas increase
de amoniaco
(2.0 M) junto con sulfuro de amonio,
in nuclearity as the pH of the solution
posteriormente
son
adicionados
acido the
clorh
drico ysynthesis
MoO3 .
decreases. This means that traditionally,
aqueous
En
un
cuarto
tubo
de
ensayo
se
adiciona
1.0
mL
de the
la
of the POM cluster is the norm, and as such can be in
soluci
o
n
de
(NH
)
Mo
O
junto
con
a

cido
sulf
u
rico
2.0
4 6metal
7 cations;
24
presence of simple
however, this approach can
M
tiocianato
de potasio,
finalmente
se adicionan
unas
beyextended
to organic
cations,
and the solvent
system can
be
gotas
de
cloruro
de
esta
n
o.
El
quinto
experimento
es
extended to an aqueous/organic solvent mixture; for example,
an
alogo al3CN.
anterior,
en donde
se reemplaza
el importance
tiocianato
water/CH
The synthetic
variables
of greatest
por
per
o
xido
de
hidr
o
geno
(3
%).
Finalmente
usando
la
in synthesizing such clusters are, in no particular
order:
misma
soluci
o
n
de
los
ensayos
anteriores
se
acidifica
la
1) concentration/type of metal oxide anion, 2) pH, 3) ionic
misma
con4)a
cido ntricotype/concentration,
2.0 M y se agregan
gotas
strength,
heteroatom
5) unas
presence
of
de
NH
H
PO
.
additional
6) reducing agent, and 7) temperature of
4 2 ligands,
4
reaction
and del
processing
(e.g.
microwave,
hydrothermal,
El estudio
vanadio se
realiza
con cuatro
reacciones
refluxing).
In
particular,
the
following
recent
developments
las cuales usan como partida pocos miligramos
de metain the synthesis
of POMsEn
canun
be primer
used to search
forensayo
new POM
vanadato
de amonio.
tubo de
se
systems: el s
adicionan
olido, 2.0 mL de NaOH seguidos de unas
1) The
of protonated
ammonium
cationsoresults
gotas
deuse
HCl,
observandoorganic
los cambios
de coloraci
n. El
in
an
inverse
cation
templation
effect,
which
has
been
siguiente ensayo se realiza disolviendo el s
olido
enused
5.0
[10]
[14]
POM
clusters,
hybrids,
and
framemL to
deassemble
HCl, la new
soluci
o
n
se
calienta
en
ba
n
o
de
Mar
a.
[15]
work
Luego
dematerials.
algunos minutos, se enfra y se adicionan 10.0
2) The
application
of u
strategies can lead
to the
mL
de agua.
En los
mixed-solvent
ltimos dos experimentos
se realiza
isolation of new clusters, for example, a sulfite-based
polyoxomolybdate[16] and [(P2O7)W17O51]4 .[17]

 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.angewandte.org

1739

Polioxometalatos 3/5

la disolucion en
acido sulfurico 6.0 M, en el primero se
adiciona una peque
na cantidad de sulfito de sodio, y en
el segundo zinc.

2. Resultados y Discusi
on
2.1 Preparaci
on del ion molecular Heptamolibdato.
Al disolver MO3 en medio basico y tras dar tiempo
para reaccion, al adicionar acido ocurrir
an las siguientes
reacciones:
Al interartuar con base
MO3 + 2 OH MoO42 + H2 O
(1)
Al interactuar con a
cido
7 MoO4

+ 8 H Mo7 O24

+ 4 H2 O

Los sistemas con molibdatos presentes son muy sensibles

a la carga del medio, por lo que cambios en la misma o
en el pH haran en particular que el ion heptamolibdato
desaparezca produciendo otras estructuras[1], es el ion
heptamolibdato la especie dominante en soluci
on acuosa
en pH de 3 a 5.5.[1]
En 1950 Lindqvist reporto el estudio de la estructura
cristalina del amonio heptamolibdato (NH4 )6 [Mo7024 ]4 H2 O,
donde mostraba la localizacion de siete atomos independientes de molibdeno y aunque no fue en sus das capaz de
determinar la estructura y posicion de los otros oxgenos
propuso en sano razonamiento las distancias de enlace
molibdeno oxigeno y par
ametros de celda unitaria para
la cristalizacion sin embargo no fue hasta que Evans y
Howard en 1968 con apoyo de la tecnica de difraccion
de rayos X en tres dimensiones modelaran la estructura
del ion heptamolibdato Mo7 O24 6 reportandola como se
muestra en Figura 5 [2]:

Sin embargo en el precipitado se pueden encontrar tambien otras formas mas estables dado el pH de la solucion
como lo son 7 MoO3 nH2 O o el MoO2+2

2.2 Preparaci
on de azul de molibdeno
En terminos generales el azul de molibdeno es una sustancia que tiene molibdeno con un estado de oxidacion
entre +5 y +6, el azul de molibdeno es ampliamente
utilizado en la qumica analtica y cataltica siendo una
prueba sensitiva para determinar la presencia de agentes
reductores, este compuestos no son uniformes, se encuentran en forma coloidal y de acuerdo a su forma
de produccion tienes diferentes composiciones y estructuras, estas sustancias son mejor referidas como azules
de heteropolimolibdato y aunque en desuso actualmente,

Figura 5. Vista oblicua de el ion molecular

heptamolibdato Mo7 O24 6 .

Figura 6. Durante la reacci

on y el tratamiento con

medio basico y acido. Precipitado del ion

Heptamolibdato Mo7 O24 6 .
hist
oricamente fueron usadas como pigmentos. Las caractersticas de estos compuesto no fue bien entendida
hasta llegado el a
no 1995. La preparacion usando zinc
metalico aporta electrones producto de la oxidaci
on del
mismo, utilizandose en ultimas como agente reductor. La
ligera coloracion azul pone de manifiesto la presencia de
Molibdeno en estados de oxidaci
on +5 o +6. Al agregar
Zinc en estado metalico este se comporta como agente
reductor detonando la coloracion azul del producto.

2.3 Reacci
on de

3. Conclusiones
Notas y Referencias
[1]

Lipscomb, W., Maruani, J. (n.d.). Polyoxomelates:

From platonic solids to anti-retroviral activity. (M.
Pope A. M
uller, Eds.). Harvard.

[2]

Howard, J. Evans, T. (1968). Refined molecular structure of the heptamolybdate and hexamolybdotellu-

Polioxometalatos 4/5

Figura 10

Figura 7. Antes del tratamiento

acido, producto tras la

reaccion y Azul de molibdeno, en presencia de un agente

reductor.

Figura 11
Figura 8

rate ions. Journal of the American Chemical Society,

1291(4), 32753276.
[3]
[4]
[5]

Figura 9

[6]

Long, D.-L.; Tsunashima, R.; Cronin, L. Polyoxometalates: Building Blocks for Functional Nanoscale
Systems. Angewandte Chemie International Edition
2010, 49 (10), 17361758.

[7]

Greenwood, N. N.; Earnshaw, A. Chemistry of the

Elements; Butterworth Heinemann: Oxford, 1998; p.
1007-1069.

[8]

Berzelius J.J., Poggend. Ann. Phys. Chem., 1826, 6,

p. 369

[9]

Che, M., G., P. From Scheele and Berzelius to M

uller:
Polyoxometalates (POMs) Revisited and the Missing Link between the Bottom up and Top down
Approaches. LActualite Chimique 2006, 298, 922.

Polioxometalatos 5/5

[10]

Ganapathy, S.; Fournier, M.; Paul, J. F.; Delevoye,

L.; Guelton, M.; Amoureux, J. P. Location of Protons
in Anhydrous Keggin Heteropolyacids H3 PMo12 O40
and H3 PW12 O40 by 1 H{31 P}/31 P{1 H} REDOR
NMR and DFT Quantum Chemical Calculations.
Journal of the American Chemical Society 2002, 124
(26), 78217828.