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Transition Metal Carbonyl Cluster Compounds

Design, Synthesis and Characterization of Metal Carbonyl Clusters as Molecular Metal Nanoparticles.
On the left: a nanometric molecular metal carbonyl cluster. On the right: some typical crystal packings of Pt carbonyl clusters.

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.

Useful information on ultra-small metal nanoparticles can be obtained by studying the electronic, spectroscopic, magnetic, structural and chemical properties of large molecular clusters and, among them, higher nuclearity MCCs. It is of particular interest to understand how the physical properties of metal aggregates change with their increasing sizes, and when the molecular behaviour fades into a bulk-like one.

Major efforts must be done in order to prepare and characterise larger and larger MCCs with different compositions. 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. This point has been confirmed also for the three examples of Au nano-clusters whose structures have been up to now determined.

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 well-defined 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.

Staff

  • Prof Maria Carmela Iapalucci
  • Prof Cristina Femoni
  • Prof Stefano Zacchini
  • Dr Iacopo Ciabatti
  • Dr Cristiana Cesari
  • Dr Chiara Capacci
  • Dr Silvia Ruggieri

Collaborations

  • Dr Tiziana Funaioli, Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Italia, Studio delle proprietà di multivalenza in cluster carbonilici ad elevata nuclearità mediante tecniche elettrochimiche e spettroelettrochimiche.
  • Prof M. Riccò, Dipartimento di Fisica, Università di Parma, Italia, Determinazione delle proprietà magnetiche ed elettriche allo stato solido in cluster carbonilici.
  • Dr Marco Bortoluzzi, Dipartimento di Scienze Molecolari e Nanosistemi, Ca' Foscari University of Venice, Italia, Studi teorici e calcoli DFT su cluster molecolari.

Contacts

Maria Carmela Iapalucci

Associate Professor

Dipartimento di Chimica Industriale "Toso Montanari" - CHIMIND

Viale del Risorgimento 4

Bologna (BO)

tel: +39 051 20 9 3705

tel: +39 051 20 9 3697

fax: +39 051 20 9 3690

Cristina Femoni

Associate Professor

Dipartimento di Chimica Industriale "Toso Montanari" - CHIMIND

Viale del Risorgimento 4

Bologna (BO)

tel: +39 051 20 9 3629

tel: +30 0512093697

fax: +39 051 20 9 3690

Stefano Zacchini

Professor

Dipartimento di Chimica Industriale "Toso Montanari" - CHIMIND

Viale del Risorgimento 4

Bologna (BO)

tel: +39 051 20 9 3711

tel: +39 051 20 9 3697