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

• Published in: Journal of the American Chemical Society Vol. 128; no. 37; pp. 12243 - 12255
• Main Authors: Sénéchal-David, Katell, Hemeryck, Anne, Tancrez, Nicolas, Toupet, Loïc, Williams, J. A. Gareth, Ledoux, Isabelle, Zyss, Joseph, Boucekkine, Abdou, Guégan, Jean-Paul, Le Bozec, Hubert, Maury, Olivier
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.09.2006; Amer Chemical Soc
• Subjects: Chemical Sciences; Chemistry; Chemistry, Multidisciplinary; Exact sciences and technology; General and physical chemistry; Heterocyclic compounds; Heterocyclic compounds with several n hetero atoms in the same ring, in separated rings or in fused rings; Inorganic chemistry; or physical chemistry; Organic chemistry; Physical Sciences; Preparations and properties; Science & Technology; Theoretical and; IR(III) COMPLEXES; METALLOORGANIC COMPOUNDS; METAL-ION; CHROMOPHORES; MOLECULAR HYPERPOLARIZABILITIES; ORGANOMETALLIC COMPLEXES; QUADRATIC HYPERPOLARIZABILITY; NITRATE COMPLEXES; DENSITY-FUNCTIONAL THEORY; CHARGE-TRANSFER; Harmonic; Chemical solution; Nitrogen heterocycle; Ligand; Light scattering; Rare earth metal complex; Gadolinium complex; Non linear optics; Theoretical study; Transition metal; NMR spectrometry; X ray diffraction; Optimization; Intramolecular charge transfer; Solid state; Lanthanide ion; Transition energy; Optical properties; Density functional method; Chemical synthesis; Yttrium; Structural analysis; Ultraviolet visible spectrometry
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja063586j

The synthesis and structural, photophysical, and second-order nonlinear optical (NLO) properties of a novel lanthanide terpyridyl-like complex family LLn(NO3)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 thourougly 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 β, 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.