title: Synthesis, structural studies, theoretical calculations, and linear and nonlinear optical properties of terpyridyl lanthanide complexes: new evidence for the contribution of f electrons to the NLO activity.
abstract: The synthesis and structural, photophysical, and second-order nonlinear optical (NLO) properties of a novel lanthanide terpyridyl-like complex family LLn(NO(3))(3) (Ln = La, Gd, Dy, Yb, and Y) are reported. The isostructural character of this series in solution and in the solid state has been established on the basis of X-ray diffraction analysis in the cases of yttrium and gadolinium complexes, theoretical optimization of geometry (DFT), and NMR spectroscopy. The absorption, emission, and solvatochromic properties of the free terpyridyl-like ligand L were thoroughly investigated, and the twist intramolecular charge transfer (TICT) character of the lowest energy transition was confirmed by theoretical calculation (TDDFT and CIS). The similar ionochromic effect of the different lanthanide ions was evidenced by the similar UV-visible spectra of the complete family of complexes. On the other hand, the quadratic hyperpolarizability coefficient beta, measured by the harmonic light scattering (HLS) technique, is clearly dependent on the nature of the metal, and a careful examination of the particular case of yttrium unambiguously confirms the contribution of metal f electrons to the NLO activity.
authors.affiliation: Laboratoire de Chimie de Coordination et Catalyse, UMR 6509 CNRS-Université Rennes 1, Institut de Chimie, Campus de Beaulieu, 35042 Rennes Cedex, France.
authors.forename: Katell
authors.initials: K
authors.lastname: Sénéchal-David
authors.forename: Anne
authors.initials: A
authors.lastname: Hemeryck
authors.forename: Nicolas
authors.initials: N
authors.lastname: Tancrez
authors.forename: Loïc
authors.initials: L
authors.lastname: Toupet
authors.forename: J A Gareth
authors.initials: JA
authors.lastname: Williams
authors.forename: Isabelle
authors.initials: I
authors.lastname: Ledoux
authors.forename: Joseph
authors.initials: J
authors.lastname: Zyss
authors.forename: Abdou
authors.initials: A
authors.lastname: Boucekkine
authors.forename: Jean-Paul
authors.initials: JP
authors.lastname: Guégan
authors.forename: Hubert
authors.initials: H
authors.lastname: Le Bozec
authors.forename: Olivier
authors.initials: O
authors.lastname: Maury