title: Strongly Circularly Polarized Emission from Water-Soluble Eu(III)- and Tb(III)-Based Complexes: A Structural and Spectroscopic Study.
abstract: Water-soluble Eu(III) and Tb(III) complexes with N,N'-bis(2-pyridylmethyl)-trans-1,2-diaminocyclohexane-N,N'-diacetic acid (H2bpcd) have been synthesized and characterized in their racemic and enantiopure forms. The ligand has been designed to bind Ln(III) ions, providing a dissymmetric environment able to solicit strong chiroptical features while at the same time leaving a few coordination sites available for engaging further ancillary ligands. Potentiometric studies show that Ln(III) complexes have a relatively good stability and that at pH 7 the [Ln(bpcd)]+species is largely dominant. DFT calculations carried out on the (S,S)-[Y(bpcd)(H2O)5]+complexes (the closed-shell equivalents of [Eu(bpcd)(H2O)5]+and [Tb(bpcd)(H2O)5]+) indicate that the two trans-O,O and trans-Npy,Npyconfigurations are equally stable in solution and present two coordinated water molecules. This is in agreement with the hydration number ∼2.6 determined by luminescence lifetime measurements on Tb(III) and Eu(III) complexes. A detailed optical and chiroptical spectroscopic characterization has been carried out and reveals that the complexes display an efficient luminescence in the visible spectral range accompanied by a strong CPL activity. A value for glum(around 0.1 on the top of the 546 nm band) for the Tb-based complex has been found. This is one of the highest glumvalues measured up to now for chiral Tb complexes. These results suggest that in principle Tb(bpcd)Cl is suitable to be employed as a CPL bioprobe for relevant analytes in aqueous media.
authors.affiliation: Luminescent Materials Laboratory, DB, Università di Verona, and INSTM, UdR Verona , Strada Le Grazie 15, 37134 Verona, Italy.
authors.forename: Marco
authors.initials: M
authors.lastname: Leonzio
authors.affiliation: Dipartimento Politecnico di Ingegneria e Architettura, Laboratorio di Tecnologie Chimiche, Università di Udine , via Cotonificio 108, 33100 Udine, Italy.
authors.forename: Andrea
authors.initials: A
authors.lastname: Melchior
authors.affiliation: Dipartimento Politecnico di Ingegneria e Architettura, Laboratorio di Tecnologie Chimiche, Università di Udine , via Cotonificio 108, 33100 Udine, Italy.
authors.forename: Georgina
authors.identifier: http://orcid.org/0000-0001-5420-471X
authors.initials: G
authors.lastname: Faura
authors.affiliation: Dipartimento Politecnico di Ingegneria e Architettura, Laboratorio di Tecnologie Chimiche, Università di Udine , via Cotonificio 108, 33100 Udine, Italy.
authors.forename: Marilena
authors.initials: M
authors.lastname: Tolazzi
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa , via Moruzzi 13, 56124 Pisa, Italy.
authors.forename: Francesco
authors.initials: F
authors.lastname: Zinna
authors.affiliation: Dipartimento di Chimica e Chimica Industriale, Università di Pisa , via Moruzzi 13, 56124 Pisa, Italy.
authors.forename: Lorenzo
authors.identifier: http://orcid.org/0000-0003-2347-2150
authors.initials: L
authors.lastname: Di Bari
authors.affiliation: Luminescent Materials Laboratory, DB, Università di Verona, and INSTM, UdR Verona , Strada Le Grazie 15, 37134 Verona, Italy.
authors.forename: Fabio
authors.identifier: http://orcid.org/0000-0003-0349-1960
authors.initials: F
authors.lastname: Piccinelli