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Supervisors:  Prof. Fabio Marchetti

Title:  Synthesis of organometallic ruthenium and iridium complexes and investigation of their potential as water oxidation catalysts

Abstract: Artificial photosynthesis enables the possibility of generating clean and sustainable energy resources through water splitting. Although numerous strategies are reported, the main drawback to efficient solar water splitting is the development of robust and long-lasting water oxidation catalysts.
The aim of this project is the design and the synthesis of novel ruthenium and iridium complexes as potential water oxidation catalysts.
We have synthesised new ruthenium complexes with variable N-chelating ligands and containing two metal centres, respectively playing a photosensitive and a catalytic role.; a new mononuclear ruthenium complex with a pentadentate ligand based on phenanthroline; and more recently we have prepared iridium complexes containing cyclopentadienyl ligands variably sybstituted.
All the prepared compounds have been characterized by spectroscopic and analytical techniques and their activity in water oxidation catalysis has been evaluated in collaboration with prof. Sebastiano Campagna (University of Messina), prof. Antoni Llobet (ICIQ of Tarragona) and prof. Alceo Macchioni (University of Perugia).

Publications:
- Construction of a Functionalized Selenophene‐Allylidene Ligand via Alkyne Double Action at a Diiron Complex,
A. De Palo, S. Zacchini, G. Pampaloni, F. Marchetti, EurJIC, 2020, 34, 3268-3276.
- Ru (II) water oxidation catalysts with 2, 3-bis (2-pyridyl) pyrazine and tris (pyrazolyl) methane ligands: assembly of photo-active and catalytically active subunits in a dinuclear structure,
A. De Palo, G. La Ganga, F. Nastasi, M. Guelfi, M. Bortoluzzi, G. Pampaloni, Dalt. Trans. 2020, 49, 3341-3352.
- A biotin-conjugated photo-activated CO-releasing molecule (biotinCORM): efficient CO-release from an avidin–biotinCORM protein adduct,
J.S. Ward, A. De Palo, B.J. Aucott, J.W.B. Moir, J.M. Lynam, I.J.S. Fairlamb, Dalt. Trans. 2019, 48, 16233-16241.
- Synthesis and spectroscopic/DFT structural characterization of coordination compounds of Nb (V) and Ti (IV) with bioactive carboxylic acids,
A. De Palo, L. Biancalana, M. Bortoluzzi, M.A. Martini, F. Marchetti, Polyhedron, 2018, 141, 208-214.
- A general strategy to add diversity to ruthenium arene complexes with bioactive organic compounds via a coordinated (4-hydroxyphenyl) diphenylphosphine ligand,
L. Biancalana, L. K. Batchelor, A. De Palo, S. Zacchini, G. Pampaloni, P. J Dyson, F. Marchetti, Dalt. Trans. 2017, 46, 11973.

Oral communications at congress:

- XLVII National Conference of the Inorganic Division of the talian Chemistry Society (SCI), September 9^th-12^th 2019, Bari, Italy.
Synthesis and investigation of new iridium complexes containing tetramethylcyclopentadienyl ligands variably substituted as potential catalysts for water oxidation.
- CFF 2019 - Chemistry for the Future, July 3^rd -5^th July 2019, Pisa, Italy.
Synthesis and characterization of ruthenium(II) and iridium (III) complexes as potential catalysts for water oxidation.

Poster communications at congress:
- XI International School of Organometallic Chemistry (ISOC 2017), September 2^nd-6^th 2017, San Benedetto del Tronto, Italy.
Design and synthesis of dinuclear ruthenium(II) complexes with polyazotate bridging ligands toward artificial photosynthetic systems.
- Chemistry for the Future, July 4^th-6^th 2018, Department of Chemistry and Industrial Chemistry, Pisa, Italy.
Design and synthesis of dinuclearruthenium(II) complexes with polyazotate bridging ligands as potential water oxidation catalysts.
- 28th International Conference on Organometallic Chemistry (ICOMC-2018), July 15^th-20^th, Florence, Italy.
Design and synthesis of dinuclearruthenium(II) complexes with polyazotate bridging ligands as potential water oxidation catalysts.
- 20th IUPAC International Symposium on Organometallic Chemistry Directed towards Organic Synthesis, July 21^st-25^th, Heidelberg, Germany.
Synthesis of Dinuclear Ruthenium(II) Complexes Containing N-Donor Bridging Ligands as Potential Dye-Catalyst Assemblies for Water Oxidation and Investigation of their Electrochemical Properties.