Fluorinated β-Diketonate Diglyme Lanthanide Complexes as New Second-Order Nonlinear Optical Chromophores: The Role of f Electrons in the Dipolar and Octupolar Contribution to Quadratic Hyperpolarizability
| Autor: | R. Ugo, Stefania Righetto, Graziella Malandrino, Dominique Roberto, Elena Cariati, Leonardo Belpassi, Maria Elena Fragala, Joseph Zyss, Filippo De Angelis, Francesca Tessore, Isabelle Ledoux-Rak, I. L. Fragala, Adriana Valore, Khuyen Hoang Thi |
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| Rok vydání: | 2010 |
| Předmět: |
Methyl Ethers
Models Molecular Lanthanide Optics and Photonics Hyperpolarizability Electron Lanthanoid Series Elements Biochemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry Models Computational chemistry Electrochemistry Organometallic Compounds Ethylene Glycols Ketones Chemistry Molecular Second-harmonic generation Diglyme General Chemistry Chromophore Dipole Physical chemistry Luminescence |
| Zdroj: | Journal of the American Chemical Society 132 (2010): 4966–4970. info:cnr-pdr/source/autori:Valore, A.; Cariati, E.; Righetto, S.; Roberto, D.; Tessore, F.; Ugo, R.; Fragala, I.L.; Fragala, M.E.; Malandrino, G.; De Angelis, F.; Belpassi, L.; Ledoux-Rak, I.; Thi, K.H.; Zyss, J./titolo:Fluorinated beta-Diketonate Diglyme Lanthanide Complexes as New Second-Order Nonlinear Optical Chromophores: The Role of f Electrons in the Dipolar and Octupolar Contribution to Quadratic Hyperpolarizability/doi:/rivista:Journal of the American Chemical Society (Print)/anno:2010/pagina_da:4966/pagina_a:4970/intervallo_pagine:4966–4970/volume:132 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | The second-order nonlinear optical (NLO) properties of [Ln(hfac)(3)(diglyme)] (hfac = hexafluoroacetylacetonate; diglyme = bis(2-methoxyethyl)ether; Ln = La, Ce, Pr, Sm, Eu, Gd, Er, Lu) complexes have been investigated by a combination of electric-field second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques, providing evidence for the relevant role of f electrons in tuning the second-order NLO response dominated by the octupolar contribution. These lanthanide NLO chromophores allow a clean valuation of the influence of f electrons on the quadratic hyperpolarizability and on its dipolar and octupolar contributions. Molecular quadratic hyperpolarizability values measured by the EFISH method, beta(EFISH), initially increase rapidly with the number of f electrons, the value for the Gd complex being 11 times that of the La complex, whereas this increase is much lower for the last seven f electrons, the beta(EFISH) value of the Lu complex being only 1.2 times that of the Gd complex. The increase of , which is dominated by an octupolar contribution, is much lower along the Ln series. Remarkably, the good values of these simple systems, well known for their luminescence properties, are reached at no cost of transparency. |
| Databáze: | OpenAIRE |
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