Table Of ContentPolyoxometalate Chemistry
for Nano-Composite Design
Nanostructure Science and Technology
Series Editor: David J. Lockwood, FRSC
National Research Council of Canada
Ottawa, Ontario, Canada
Current volumes in this series:
Polyoxometalate Chemistry for Nano-Composite Design
Edited by Toshihiro Yamase and Michael T. Pope
Self-Assembled Nanostructures
Jin Zhang, Zhong-lin Wang, Jun Liu, Shaowei Chen, and Gang-yu Liu
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publisher.
Polyoxometalate Chemistry
for Nano-Composite Design
Edited by
Toshihiro Yamase
Chemical Resources Laboratory
Tokyo Institute of Technology
Yokohama, Japan
and
Michael T. Pope
Department of Chemistry
Georgetown University
Washington, DC
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PREFACE
Polyoxometalates are discrete early transition metal-oxide cluster anions and comprise
a class of inorganic complexes of unrivaled versatility and structural variation in both
symmetry and size, with applications in many fields of science. Recent findings of both
electron-transfer processes and magnetic exchange-interactions in polyoxometalates with
increasing nuclearities, topologies, and dimensionalities, and with combinations of different
magnetic metal ions and/or organic moieties in the same lattice attract strong attention
towards the design of nano-composites, since the assemblies of metal-oxide lattices ranging
from insulators to superconductors form the basis of electronic devices and machines in
present-day industries. The editors organized the symposium, “Polyoxometalate Chemistry
for Nano-Composite Design” at the Pacifichem 2000 Congress, held in Honolulu on
December 17–19, 2000. Chemists from several international polyoxometalate research
groups discussed recent results, including: controlled self-organization processes for the
preparation of nano-composites; electronic interactions in magnetic mixed-valence
cryptands and coronands; synthesis of the novel polyoxometalates with topological or
biological significance; systematic investigations in acid-base and/or redox catalysis for
organic transformations; and electronic properties in materials science.
It became evident during the symposium that the rapidly growing field of
polyoxometalates has important properties pertinent to nano-composites. It is therefore easy
for polyoxometalate chemists to envisage a “bottom-up” approach for their design starting
from individual small-size molecules and moieties which possess their own functionalities
relevant to electronic/magnetic devices (ferromagnetism, semiconductivity, proton-
conductivity, and display), medicine (antitumoral, antiviral, and antimicrobacterial
activities), and catalysis. The resulting exchange of ideas in the symposium has served to
stimulate progress in numerous interdisciplinary areas of research: crystal physics and
chemistry, materials science, bioinorganic chemistry (biomineralization), and catalysis.
Each participant who contributed to this text highlights some of the more interesting and
important recent results and points out some of the directions and challenges of future
research for the controlled linking of simple (molecular) building blocks, a reaction with
which one can create mesoscopic cavities and display specifically desired properties. We
believe that this volume provides an overview of recent progress relating to
polyoxometalate chemistry, but we have deliberately chosen to exclude discussion of
infinite metal oxide assemblies.
Acknowledgment. The editors would like to thank Nissan Chemical Industries, Ltd.,
Rigaku, and the Donors of the Petroleum Research Fund of the American Chemical Society
for contributions towards the support of the Symposium.
Toshihiro Yamase
Michael T. Pope
v
CONTENTS
SELF-ASSEMBLY AND NANOSTRUCTURES
Chemistry with Nanoparticles: Linking ofRing- and Ball-shaped Species 1
P. Kögerler and A. Müller
Prospects for Rational Assembly of CompositePolyoxometalates 17
N. Belai, M. H. Dickman, K.-C. Kim, A. Ostuni, M. T. Pope, M. Sadakane,
J. L. Samonte, G. Sazani, and K. Wassermann
Composite Materials Derived from Oxovanadium Sulfates 27
M. I. Khan, S. Cevik, and R. J. Doedens
Solid State Coordination Chemistry: Bimetallic Organophosphonate Oxide Phases
of the Family (M=V, Mo) 39
R. C. Finn and J. Zubieta
PolyoxothiomolybdatesDerived from the BuildingUnit 59
F. Sécheresse, E. Cadot, A. Dolbecq-Bastin, and B. Salignac
Lanthanide Polyoxometalates: Building Blocks for New Materials 73
Q. Luo, R. C. Howell, and L. C. Francesconi
ORGANOMETALLIC OXIDES AND SOLUTION CHEMISTRY
Dynamics of Organometallic Oxides: From Synthesis and Reactivity to DFT
Calculations 83
V. Artero, A. Proust, M.-M. Rohmer, and M. Bénard
An Organorhodium Tungsten Oxide Cluster with a Windmill-like Skeleton:
Synthesis of and DirectObservation by ESI-MS ofan
Unstable Intermediate 97
K. Nishikawa, K. Kido, J. Yoshida, T. Nishioka, I. Kinoshita, B. K. Breedlove,
Y. Hayashi, A. Uehara, and K. Isobe
Role of Alkali-metal Cation Size in Electron Transfer to Solvent-separated 1:1
Ion Pairs 103
I. A. Weinstock, V. A. Grigoriev, D. Cheng, and C. L. Hill
vii
viii CONTENTS
New Classes ofFunctionalized Polyoxometalates: Organo-nitrogen Derivatives of
Lindqvist Systems 129
A. R. Moore, H. Kwen, C. G. Hamaker, T. R. Mohs, A. M. Beatty, B. Harmon,
K. Needham, and E. A. Maatta
Polyoxometalate Speciation—Ionic Medium Dependence and Complexation to
Medium Ions 139
L. Pettersson
Some Smaller Polyoxoanions: Their Synthesis and Characterization in Solution 149
H. Nakano, T. Ozeki, and A. Yagasaki
MAGNETIC, BIOLOGICAL, AND CATALYTIC INTERACTIONS
Polyoxometalates: From Magnetic Models to Multifunctional Materials 157
J. M. Clemente-Juan, M. Clemente-León, E. Coronado, A. Forment, A. Gaita,
C. J. Gómez-García, and E. Martínez-Ferrero
Magnetic Exchange Coupling and Potent Antiviral Activity of
169
T. Yamase, B. Botar, E. Ishikawa, K. Fukaya, and S. Shigeta
Tetravanadate, Decavanadate, Keggin and Dawson Oxotungstates Inhibit Growth
of S. cerevisiae 181
D. C. Crans, H. S. Bedi, S. Li, B. Zhang, K. Nomiya, N. C. Kasuga, Y. Nemoto,
K. Nomura, K. Hashino, Y. Sakai, Y. Tekeste, G. Sebel,L.-A. E. Minasi,
J. J. Smee, and G. R. Willsky
Selective Oxidation of Hydrocarbons with Molecular Oxygen Catalyzed by
Transition-metal-substituted Silicotungstates 197
N. Mizuno, M. Hashimoto, Y. Sumida, Y. Nakagawa, and K. Kamata
Transition-metal-substituted Heteropoly Anions in NonpolarSolvents—Structures
and Interaction with Carbon Dioxide 205
J. Paul, P. Page, P. Sauers, K. Ertel, C. Pasternak, W. Lin, and M. Kozik
Polyoxometalates and Solid State Reactions at Low Heating Temperatures 217
S. Jing, F. Xin, and X. Xin
Structure Determination ofPolyoxotungstates Using High-energy Synchrotron
Radiation 225
T. Ozeki, N. Honma, S. Oike, and K. Kusaka
Index 233
CHEMISTRY WITH NANOPARTICLES:
LINKING OF RING- AND BALL-SHAPED SPECIES
P. Kögerler1andA.Müller2*
1Ames Laboratory
Iowa State University
Ames, IA 50011, USA
2Department of Chemistry
University of Bielefeld
33501 Bielefeld, Germany
INTRODUCTION
The fabrication of well-ordered arrays of well-defined nanoparticles or clusters is of
fundamental and technological interest. As this is a difficult task, different techniques have
been employed.1 An elegant approach would be to link well-defined building blocks in a
chemically straightforward procedure yielding a monodisperse or a completely homo-
geneous material. We succeeded now to cross-link assembled nanosized metal-oxide-based
clusters/composites – novel supramolecular entities – under one-pot conditions.
Pertinent targets include the synthesis of materials with network structures that have
desirable and predictable properties, such as mesoporosity2 (due to well-defined cavities
and channels), electronic and ionic transport,3 ferro- as well as ferrielasticity, luminescence
and catalytic activity.4 The synthesis of solids from pre-organized linkable building blocks
with well-defined geometries and chemical properties is, therefore, of special interest.5 In
this article, we will focus on the relationship between some polyoxomolybdate-based
wheel- and ball-shaped clusters and network structures derived from these precursors.6
Accordingly, a strategy will be presented that allows the intentional synthesis of solid-state
materials, both by designing and utilizing known clusters that can be treated as synthon-
based building blocks (and thus these synthons can be linked together), with preferred
structure and function.
Polyoxometalate Chemistry for Nano-Composite Design
EditedbyYamase andPope,KluwerAcademic/PlenumPublishers,2002 1
2 P. Kögerler and A. Müller
BUILDING BLOCKS OF THE NANOPARTICLES
The basic cluster entities – the synthons – involved in this approach can furthermore
be decomposed to characteristical transferable building groups.7 For instance, building
blocks containing 17 molybdenum atoms can be given as an example of a
generally repeated building block or synthon which can be considered to form anions
consisting of two or three of these units. The resulting species are of the type (e.g.,
1, a two-fragment cluster, or
of the type (e.g., 2, a
three-fragment cluster, see Figure 1.8 It has now been well
established that a solution containing species can be reduced and
acidified further to yield a mixed-valence wheel-shaped cluster (and derivatives thereof)
3 (due to inherent problems with the
determination of the exact composition, the initially published formula9 was flawed with
regard to the reduction and protonation grade).10 Formally, this cluster can be regarded as a
tetradecamer with symmetry (if the hydrogen atoms are excluded) and structurally
generated by linking 140 octahedra and 14 pentagonal bipyramids.
Using the general building block principle for this “classical” giant-wheel-type cluster
the structural building blocks for other ring-shaped clusters can be deduced and expressed
in terms of the three different building blocks as (n = 14). The
building blocks of the type and are each present 14 times in the
“original” cluster and the corresponding analogous (synthesized without the NO ligands)
isopolyoxometalate cluster 4 (having 14 instead of
Chemistry with Nanoparticles 3
14 groups) which turned out to comprise the prototype of the soluble
molybdenum blue species.10 Furthermore, a larger “giant-wheel” cluster with
symmetry can also be synthesized under similar conditions; the larger cluster geometrically
results if two more of each of the three different types of building units are (formally)
added to the “giant-wheel” cluster.11 This presents a hexadecameric ring structure,
containing 16 (n = 16) instead of 14 of each of the three aforementioned building blocks
(Figure 2).
This consideration is interesting from the point of view that it is possible to express the
architecture of these systems with a type of Aufbau principle. Furthermore, the
symmetrical group can be subdivided again into one and two units
(i.e. two groups linked by an It is interesting to notethat the
building blocks are found in many other large polyoxometalate structures and
itself can be divided into a (close-packed) pentagonal group – built up
by a central pentagonal bipyramid sharing edges with five octahedra – and
two more octahedra sharing corners with atoms of the pentagon (Figure 3). The
mentioned pentagonal group comprises a necessary structural motif to
construct spherical systems: while twelve edge-sharing (regular) pentagons form a
dodecahedron the introductionoflinkers inbetween the pentagons resultsin
an extended structure that preserves the symmetry (Figure 4). In
this so-called Keplerate-type structure the centers of the pentagons define the vertices of an
icosahedron while the centers of the linker units define the vertices of an icosidodecahedron.
