functional aspects of metal carbonyl clusters

Research Group n. 3
UNIVERSITA’ di Bologna
FUNCTIONAL ASPECTS OF METAL CARBONYL CLUSTERS
Cristina Femoni, Maria Carmela Iapalucci and Stefano Zacchini *
Dipartimento di Chimica Industriale “Toso Montanari”, viale del Risorgimento 4, 40136 Bologna,
Italy.
*E-mail: stefano.zacchini@.unibo.it
High nuclearity molecular Metal Carbonyl Clusters (MCCs) are perfectly (atomically)
monodisperse ligand-stabilised metal nanoparticles. In fact, the largest species studied to date
already have nanometric dimensions, as for ultra-small metal nanoparticles. We have demonstrated
that the structures of molecular MCCs with 1-2 nm sizes are still heavily influenced by surface
ligands and their metal cores are rather deformable, as in the case of Au nano-clusters.
The electrochemical behaviour of large MCCs is in keeping with incoming metalisation of their
metal cores as the nuclearity increases. Besides, to fully understand their NMR and magnetic
behaviour is still a major goal.
Moreover, MCCs can be assembled into molecular wires, charge-transfer materials and
nanostructured monolayers. Further applications in the field of molecular nanostructured materials
may arise by systematically investigating their self-assembly properties.
Molecularly defined MCCs are valuable precursors for the preparation of metal nanoparticles,
conducting metal nanowires (“printable metals”) and nanostructured heterogeneous catalysts, after
their controlled decomposition.
Overall, molecular MCCs may find applications as single molecular metal nanoparticles with welldefined and quantum sized physical properties, as supramolecular aggregates in the field of
molecular nanomaterials, and as precursors of perfectly defined metal nanoparticles.
In conclusion, molecular metal clusters can have a substantial impact in nanoscience and
nanotechnology by helping a better understanding of the chemical and physical phenomena
occurring in the nanoworld.
Within this framework, our work is dedicated to the synthesis and characterisation of large
molecular MCCs, the determination of their physical properties (e.g., spectroscopic, magnetic,
electrochemical properties), their use as building blocks for self-assembly and as precursors for
metal nanoparticles, metal wires and nanostructured materials. The clusters studied involve metals
of Groups 8-10 and comprise homo-, bi- and hetero-metallic species.
Keywords: cluster, carbonyl compounds, synthesis, X ray structure, magnetic behavior, redox
properties, catalysis, metal nanoparticles, nanostructured materials,
Publications:
1.
2.
M. Bortoluzzi, I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, S. Zacchini, "[H 3–
n–
(n = 1, 2) and "[H2Fe3(CO)10(IrCOD)]– Bimetallic Fe-Ir Hydride
nFe4(CO)12(IrCOD)]
Carbonyl Clusters", Organometallics, 2015, 34, 189-197.
I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, S. Zacchini, "Co5C and Co4C carbido
carbonyl clusters stabilized by [AuPPh3]+ fragments", Inorg. Chim. Acta, 2015, 428, 203-211.
3.
M. Bortoluzzi, I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, G. Longoni, S.
Zacchini, "Hydride Migration from a Triangular Face to a Tetrahedral Cavity in Tetranuclear
Iron Carbonyl Clusters upon Coordination of [AuPPh3]+ Fragments", Angew. Chem. Int. Ed.,
2014, 53, 7233-7237.
I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, A. Ienco, G. Longoni, G. Manca, S.
Zacchini, "Octahedral Co-Carbide Carbonyl Clusters Decorated by [AuPPh3]+ Fragments:
Synthesis, Structural Isomerism, and Aurophilic Interactions of Co6C(CO)12(AuPPh3)4",
Inorg. Chem., 2014, 53, 9761-9770.
M. Bortoluzzi, I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, G. Longoni, S.
Zacchini,
"Peraurated
nickel
carbide
carbonyl
clusters:
the
cationic
[Ni6(C)(CO)8(AuPPh3)8]2+monocarbide and the [Ni12(CO)(C2)(CO)17(AuPPh3)3]–anion
containing one carbide and one acetylide unit", Dalton Trans., 2014, 43, 13471-13475.
I. Ciabatti, C. Femoni, M. Gaboardi, M. C. Iapalucci, G. Longoni, D. Pontiroli, M. Riccò, "
S. Zacchini, Structural rearrangements induced by acid-base reactions in metal carbonyl
clusters: the case of [H3–nCo15Pd9C3(CO)38]n– (n = 0-3)", Dalton Trans., 2014, 43, 4388-4399.
I. Ciabatti, C. Femoni, M. C. Iapalucci, G. Longoni, S. Zacchini, "Platinum Carbonyl
Clusters Chemistry: Four Decades of Challenging Nanoscience", J. Clust. Sci., 2014, 25,
115-146.
I. Ciabatti, C. Femoni, M. Hayatifar, M. C. Iapalucci, G. Longoni, C. Pinzino, M. V. Solmi,
S. Zacchini, "The Redox Chemistry of [Co6C(CO)15]2–: A Synthetic Route to New CoCarbide Carbonyl Clusters", Inorg. Chem., 2014, 53, 3818-3831.
4.
5.
6.
7.
8.
SUPPLEMENTARY MATERIAL
Position of the components of the Research Groups
Name
Surname
Position *
Affiliation
Cristina
Femoni
PA
University of Bologna
Maria Carmela
Iapalucci
PA
University of Bologna
Stefano
Zacchini
PA
University of Bologna
Cristiana
Cesari
PoD
University of Bologna
Chiara
Capacci
PhD
University of Bologna
Silvia
Ruggieri
PhD
University of Bologna
*: PO = Full professor; PA = Associate professor; RU = University researcher; CO = contract; PoD
= Postdoctoral fellows; RC = CNR staff or other Institutions Research; T = technician, VR =
visiting researcher, S = student
Equipment
Type
Producer
Year of acquisition
Bruker-ApexII X-ray
difractometer
Bruker
2004
Technical skills




Manipulation of air sensitive compounds;
Synthesis;
X ray structure determination;
Spectroscopic characterization.

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