Abstract
In the last few years the above authors have undertaken a collaborative study of the physical and chemical properties of high-nuclearity metal cluster compounds. The collaboration was sponsored by the European Economic Community “Stimulation Action” program. In the course of these studies it has become evident that this interesting class of materials may indeed be viewed as model systems for monodisperse small metal particles, embedded in a dielectric solid. The metal cluster compounds consist of (neutral or ionic) macromolecules, each macromelecule being composed of a core of a certain number (n) of metal atoms, the core being surrounded by a shell of ligands. Since these are chemical compounds, a given compound contains macromolecules of one and the same type, and thus an assembly of identical metal cores. Consequently, the solid formed can be described as a macroscopically large sample of identical metal particles, mutually separated by the ligand shells, which provide an effective means of “chemical stabilization”.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
A. Simon, Clusters of valence electron poor metals; structure, bonding and properties, Angew. Chem. Int. Ed. Engl. 27:159 (1988).
See e.g. Ø. Fischer, Chevrel phases: superconducting and normal state properties, Appl. Phys. 27:1 (1988);
T. Hughbanks and R. Hoffman, Molybdenum chalcogenides: clusters, chains and extended solids. The approach to bonding in three dimensions, J. Am. Chem. Soc. 105:1150 (1983);
P. Gougeon, M. Potel, M. Sergent, and P. Monceau, New superconducting ternary molybdenum chalcogenides with condensed MO6n clusters, Physica 135B:386 (1985).
W. Krätschmer, L.D. Lamb, K. Fostiropoulos and D.R. Huffman, Solid C60: a new form of carbon, Nature 347:354 (1990).
G. Longoni, A. Ceriotti, M. Marchionna and G. Piro, Large molecular metal carbonyl clusters: models of metal particles, in: “Surface Organometallic Chemistry: Molecular Approaches to Surface Catalysis”, eds. J.M. Basset et al., Kluwer (1988) p. 157 (and references in this review).
G. Schmid, Metal clusters and cluster metals, Polyhedron 7:2321 (1988);
G. Schmid, Clusters and colloids: bridges between molecular and condensed material, Endeavour, New Series 14:172 (1990);
G. Schmid, Large transition metal clusters-bridges between homogeneous and heterogeneous catalysts? Aspects of homogeneous catalysis 7:1 (1990) ed. R. Ugo, Kluwer.
M.N. Vargaftik, V.P. Zagorodnikov, I.P. Stolyarov, LI. Moiseev, V.A. Likholobov, D.I. Kochubey, A.l. Chuvilin, V.l. Zaikovsky, K.I. Zamaraev, and G.I. Timofeeva, A novel giant palladium cluster, J. Chem. Soc. Chem. Commun. 937 (1985); see also the contribution of I.I. Moiseev to these proceedings.
G. Schmid, B. Morun, and J.-O. Malm, Pt309Phen*36O30±10, a, four-shell platinum cluster, Angew. Chem. Int. Ed. Engl. 28:778 (1989).
J.W.A. van der Velden, Preparation and properties of gold cluster compounds, Ph.D. thesis, Univ. of Nijmegen, The Netherlands (1983).
G. Schmid and N. Klein, Neuartige Modifikationen von Gold, Rhodium und Ruthenium — M13-cluster als Bausteine von Superclustern, Angew. Chem. 98:910 (1986);
G. Schmid, Von Metall Clustern und Clustermetallen, Nachr. Chem. Lab. 34:249 (1987).
B.J. Pronk, H.B. Brom and L.J. de Jongh, Physical properties of metal cluster compounds I: Magnetic measurements on high-nuclearity nickel and platinum clusters, Solid State Commun. 59:349 (1986).
R.E. Benfield, Magnetic properties of molecular metal clusters, in “Physics and Chemistry of Small Clusters”, eds. P. Jena et al., Plenum (1987) p.401;
R.E. Benfield, Electron paramagnetic resonance and quantumsize effects in the cluster molecule H2Os10C(CO)24, J. Phys. Chem. 91:2712 (1987);
L.J. de Jongh, Magnetic measurements on polynuclear metal cluster compounds. Between molecule and metal, Physica B 155:289 (1989).
F. Raatz and D.R. Salahub, Electronic and magnetic structure of CO on nickel clusters, Surface Science 176:219 (1986);
G.F. Holland, D.E. Ellis, and W.C. Trogler, Electronic structures of tetrahedral iron, cobalt and nickel clusters. Partial quenching of magnetism in partially carbonylated derivatives, J. Chem. Phys. 83:3507 (1985);
G. Pacchioni and P. Fantucci, Spin states and quenching of magnetism in naked and carbonylated nickel clusters, Chem. Phys. Lett. 134:407 (1987).
J.M. van Ruitenbeek, M.J.G.M. Jürgens, G. Schmid, D.A. van Leeuwen, H.W. Zandbergen and L.J. de Jongh, Metallic susceptibility in a giant molecule: Pd561Phen36O200, Proceed. 5th Int. Symp. on Small Particles and Inorg. Clusters, Konstanz, Sept. 1990, to appear in Z. Phys.D. 1991.
At the present meeting we learnt that similar results have been found by Moiseev and coworkers, see M.N. Vargaftik et al., Giant palladium clusters as catalysts of oxidative reactions of olefins and alcohols, J. Mol. Cat. 53:329 (1989).
J.M. van Ruitenbeek, Orbital magnetism in finite size systems, Proceed. 5th Int. Symp. on Small Particles and Inorg. Clusters, Konstanz, Sept. 1990, to appear in Z.Phys.D (1991).
M.P.J. van Staveren, H.B. Brom, L.J. de Jongh and G. Schmid, Physical properties of metal cluster compounds II: D.C.-conductivity of the high-nuclearity gold cluster compound Au55(PPh3)12Cl6, Solid State Commun. 60:319 (1986).
H.B. Brom, M.P.J. van Staveren and L.J. de Jongh, The AC and DC conductivity in aggregates of ligand stabilized metal-cluster molecules, Proceed. 5th Int. Symp. on Small Particles and Clusters, Konstanz, Sept. 1990, to appear in Z.Phys.D (1991).
M.P.J. van Staveren, H.B. Brom and L.J. de Jongh, Metal cluster compounds and universal features of the hopping conductivity of solids, to appear in Physics Reports (1991).
H.H.A. Smit, R.C. Thiel, L.J. de Jongh, G. Schmid and N. Klein, Physical properties of metal cluster compounds IV: The thermal motion of the Auss-core in Au55(PPh3)12Cl6 as probed by 197Au Mössbauer spectroscopy, Solid State Commun. 65:915 (1988);
H.H.A. Smit, P.R. Nugteren, R.C. Thiel and L.J. de Jongh, Mössbauer and specific heat studies of the vibrations of metal core atoms in polynuclear gold cluster compounds, Physica B153:33 (1988).
G.K. Wertheim, J. Kwo, Boon K. Teo and K.A. Keating, XPS study of bonding in ligated Au clusters, Solid State Commun. 55:357 (1985); and papers 3–6 cited by these authors.
C. Battistoni, G. Mattogno, R. Zanoni and L. Naldini, Characterisation of some gold clusters by X-ray photoelectron spectroscopy, J. Electr. Spectr. 28:23 (1982).
M.G. Mason, proceed, of this meeting; see also M.G. Mason, Electronic structure of supported small metal clusters, Phys. Rev. B27:748 (1983).
R.C. Thiel, R. Zanoni and R.E. Benfield, to be published; see also R.C. Thiel, M.W. Dirken and R. Zanoni, A reexamination of the LS. results for the cluster compound Au55(PPh3)12Cl6, Hyperf. Int. 56:1729 (1990).
R.E. Benfield, J.A. Creighton, D.G. Eadon and G. Schmid, The relationship of Au54(PPh3)12Cl6 to colloidal gold, Z. Phys. D 12:533 (1989).
U. Kreibig, Anomalous frequency and temperature dependence of the optical absorption of small gold particles, J. Phys. (Paris), coll.C2, suppl.7, 38:C2–97 (1977).
C.R.C. Wang, S. Pollack, and M.M. Kappes, Molecular excited states versus collective electronic oscillations: optical absorption probes of Na4 and Na8, Chem. Phys. Lett. 166:26 (1990).
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1992 Plenum Press, New York
About this chapter
Cite this chapter
de Jongh, L.J. et al. (1992). Physical and Chemical Properties of High-Nuclearity Metal-Cluster Compounds: Model Systems for Small Metal Particles. In: Pacchioni, G., Bagus, P.S., Parmigiani, F. (eds) Cluster Models for Surface and Bulk Phenomena. NATO ASI Series, vol 283. Springer, Boston, MA. https://doi.org/10.1007/978-1-4684-6021-6_13
Download citation
DOI: https://doi.org/10.1007/978-1-4684-6021-6_13
Publisher Name: Springer, Boston, MA
Print ISBN: 978-1-4684-6023-0
Online ISBN: 978-1-4684-6021-6
eBook Packages: Springer Book Archive