Contacts:
Supervisor(s):
Prof. Luca Labella and Prof. Simona Samaritani
Title of the PhD project:
Lanthanide/Platinum metallo-ligands: design strategies to heterometallic complexes and applications
Abstract of the PhD project:
In the last decades lanthanide(III) complexes have been highly studied due to their luminescent properties, and d-f heterometallic complexes became highly studied for the possibility of d-block metal fragments to act as antenna for an indirect excitation path. Among d-f heterometallic complexes, platinum/lanthanides complexes acquired a large interest for their medical applications as theranostic agents, related to the luminescence of the f centre and to the therapeutic platinum properties. Photophysical properties and emission temperature-dependence can be modulated controlling the coordination sphere of the two metals in the heterometallic molecular complex. Heterotopic divergent ligands having two different donor sites showing different affinity towards the two metals can drive the synthesis to heterometallic molecular, or extended structure compounds with a well-defined architecture. A high selectivity allows mild conditions in self-assembly reactions or in stepwise synthetic routes, exploiting metallo-ligand complexes. Although d-based metallo-ligands are normally used, mainly for their kinetic inertness and their well-defined coordination geometries, also the use of f-based metallo-ligands can be conveniently exploited. This synthetic approach has only a few well-documented precedents in the literature, consistently with the high complexity of lanthanide chemistry mainly directed by sterical hindrance and leading to high and variable coordination numbers. The aim of this work is to design metallo-ligands as the molecular building blocks for the construction of molecular complexes or supramolecular architectures and to use a coordination-driven approach for the synthesis of new platinum/lanthanide heterometallic complexes for possible applications for their cytotoxicity or as luminescent thermometers.
Publications:
• Bazi, M., Bracciotti, E., Fioravanti, L., Marchetti, F., Rancan, M., Armelao, L., Samaritani, S., Labella, L., "Mononuclear Rare-Earth Metalloligands Exploiting a Divergent Ligand", Inorg. Chem. 2024, 63, 17, 7678–7691. DOI: https://doi.org/10.1021/acs.inorgchem.3c04532
Oral communications at conferences
• "Lanthanide Metallo-Ligands for the Synthesis of Heteronuclear Pt2Eu2 Luminescent Arrays", Bazi, M., Samaritani, S., Labella, L., Bottaro, G., Rancan, M., Armelao, L., XLIX Congresso Nazionale di Chimica Inorganica (Italian National Convention of Inorganic Chemistry), organized by the Italian Chemical Society, Perugia, 12-15 September 2023.
Poster communications at conferences:
• "Lanthanide Metallo-Ligands for the Synthesis of Heteronuclear Pt2Eu2 Luminescent Arrays", Bazi, M., Samaritani, S., Labella, L., Bottaro, G., Rancan, M., Armelao, L., XIV International School of Organometallic Chemistry 2023, University of Camerino, 7-11 September 2023.
• "Mononuclear Rare-Earth metallo-ligands for the synthesis of Pt/RE heterometallic complexes", Bazi, M., Samaritani, S., Labella, L., Chemistry for the Future 2023, Department of Chemistry and Industrial Chemistry, University of Pisa, 28-30 June 2023.
Other achievements:
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