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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

Sénéchal-David, K.; Hemeryck, A.; Tancrez, N.; Toupet, L.; Williams, J.A.G.; Ledoux, I.; Zyss, J.; Boucekkine, A.; Guégan, J.P.; Le Bozec., H.; Maury, O.

Authors

K. Sénéchal-David

A. Hemeryck

N. Tancrez

L. Toupet

I. Ledoux

J. Zyss

A. Boucekkine

J.P. Guégan

H. Le Bozec.

O. Maury



Abstract

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.

Citation

Sénéchal-David, K., Hemeryck, A., Tancrez, N., Toupet, L., Williams, J., Ledoux, I., …Maury, O. (2006). 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. Journal of the American Chemical Society, 128(37), 12243-12255. https://doi.org/10.1021/ja063586j

Journal Article Type Article
Online Publication Date Aug 29, 2006
Publication Date 2006-09
Journal Journal of the American Chemical Society
Print ISSN 0002-7863
Electronic ISSN 1520-5126
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 128
Issue 37
Pages 12243-12255
DOI https://doi.org/10.1021/ja063586j