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Supervisors:  Prof. Lorenzo Di Bari

Title:  Development of new chiral lanthanide complexes with highly circularly polarized luminescence (CPL)

Abstract:

Chiral lanthanide (III) complexes can emit light with a high degree of circular polarization with respect to purely organic molecules (2-3 orders of magnitude higher). The emission bands are peculiar for each lanthanide ion and they are largely independent to the coordination sphere because of the f→f character of transitions involved, which are Laporte-forbidden so that consequently the direct excitation is ineffective. For this reason, a tailored design of Ln(III) complex is essential to give rise to energy transfer processes from ligand-centered excited states to lanthanide-centered excited states, through a so-called antenna effect.
The aim of this PhD project is to synthetize a set of new lanthanide complexes with both high luminescence and highly polarized emission. Our new chiral systems will be characterized by means of optical (UV-vis, fluorescence) and chiroptical (circular dichroism, circular polarized luminescence) spectroscopies in tandem with paramagnetic NMR techniques. We are interested in the applications of these systems as analytical probes, for the CPL detection of small chiral molecules, and we will also try to employ them in optoelectronic devices, including Organic Light-Emitting Diodes (OLEDs).

Publications:
- G. Pescitelli, S. Lüdeke, A.-C. Chamayou, M. Marolt, V. Justus, M. Górecki, L. Arrico, L. Di Bari, M. A. Islam, I. Gruber, M. Enamullah, C. Janiak. “Broad-range spectra analysis for chiral metal coordination compounds: (chiro)optical superspectrum of cobalt(II) complexes”, Inorganic Chemistry, 2018, 57, 21, 13397-13408.
- M. Leonzio, M. Battinelli, L. Arrico, M. Monari, L. Di Bari, F. Piccinelli. “Circularly polarized luminescence from an Eu(III) complex based on tta (2-thenoyltrifluoroacetyl-acetonate) and a tetradentate chiral ligand”, Inorganic Chemistry, 2018, 57, 16, 10257-10264.
- E. Kreidt, L. Arrico, F. Zinna, L. Di Bari, M. Seitz. “Circularly polarized luminescence in enatiopure samarium and europium cryptates”, Chem. Eur. J., 2018, 24, 51, 13556-13564.
- M. Górecki, L. Carpita, L. Arrico, F. Zinna, L. Di Bari. “Chiroptical methods in a wide wavelength range for obtaining Ln3+ complexes with circularly polarized luminescence of practical interest”, Dalton. Trans., 2018, 47, 7166-7177.
- J. Mayans, M. Font-Bardia, L. Di Bari, L. Arrico, F. Zinna, G. Pescitelli, “From mesocates to helicates: nickel(II) supramolecular assemblies derived from tetradentate Schiff bases. Structural, magnetic and chiro-optical studies”, Chem. Eur. J., 2018, 24, 30, 7653-7663.
- M. Leonzio, A. Melchior, G. Faura, M. Tolazzi, M. Bettinelli, F. Zinna, L. Arrico, L. Di Bari, F. Piccinelli, “A chiral lactate reporter based on total and circularly polarized Tb(III) luminescence”, New J. Chem., 2018, 42, 7931-7939.
- L.Arrico, G. Angelici, L. Di Bari, “Taking advantage of Co(II) induced enhanced VCD for the fast and sensitive determination of enantiomeric excess”, Org. Biomol. Chem, 2017, 15, 9800-9803.

Oral communications at congress:
- “A chiral lactate reporter based on total and circularly polarized Tb(III) luminescence”, L. Arrico, M. Leonzio, A. Melchior, G. Faura, M. Tolazzi, M. Bettinelli, F. Zinna, L. Di Bari, F. Piccinelli, XXIII International Krutyń Summer School 2018 (IKSS 2018), Krutyń (Poland), 20-26 May 2018
- “Tb(III) circularly polarized luminescence as a lactate reporter”, L. Arrico, M. Leonzio, A. Melchior, G. Faura, M. Tolazzi, M. Bettinelli, F. Zinna, L. Di Bari, F. Piccinelli, Chemistry for the Future 2017 (CfF2017), Pisa (Italy), 5-7 July 2017

Poster communications at congress:
- “Circularly polarized luminescence of complexes of Eu(III) and Sm(III) with chiral bis(oxazolinyl)pyridine”, L.Arrico, M. Górecki, L. Carpita, F. Zinna, L. Di Bari, XXXVI Convegno Interregionale Toscana – Umbria – Marche – Abruzzo della Società Chmica Italiana (TUMA 2018), Pisa (Italy), 4-5 October 2018.
- “Chiroptical methods in a wide wavelength range for obtaining Ln(III) complexes with circularly polarized luminescence of practical interest”, L.Arrico, M. Górecki, L. Carpita, F. Zinna, L. Di Bari, Chemistry for the Future 2018 (CfF 2018), Pisa (Italy), 4-6 July 2018.
- “Toward fast and sensitive determination of enantiomeric excess of chiral α-amino acids by Co(II) induced enhanced VCD”, L. Arrico, L. Di Bari, 16th International Conference on Chiroptical Spectroscopy (CD2017), Rennes (France), 11-15 June 2017.