Jean François Lamère, Isabelle Malfant, Alix Sournia-Saquet, Pascal G-Lacroix, Tahar ABBAZ, Abdel-Krim Gouasmia and Jean Marc Fabre, Lakhémici Kaboub (2007) Quadratic Nonlinear Optical Response in Partially Charged Donor-Substituted Tetrathiafulvalene: From a Computational Investigation to a Rational Synthetic Feasibility. Chemistry of Materials , 19(4), 805-815
Scientific Publications
Important: This page is frozen. New documents are now available in the digital repository DSpace
Abstract
A computational (ZINDO) investigation is employed to estimate the molecular hyperpolarizability (β) of a [(TTF-NH 2 ) 8 ] (TTF ) tetrathiafulvalene) octameric stack at various fractional (0 < F < 1) oxidation states of TTF F+ . While the neutral [(TTF-NH 2 ) 8 ] octamer exhibits a modest (7.6 × 10 -30 cm 5 esu -1 ) static β 0 value, in relation to a nearly centrosymmetric electronic structure, the formal (TTF-NH 2 ) 0.25+ oxidation state leads to a giant (β 0 ) 3891 × 10 -30 cm 5 esu -1 per octamer) NLO response. This effect
is related to the appearance of an extremely intense HOMO f LUMO-based low-lying transition, occurring at 1260 nm upon fractional oxidation, thus providing new and unexpected interest in TTF-donor substituted molecules. To illustrate the chemical feasibility of such species, two kinds of derivatives are synthesized: a TTF-dimethylaniline (TTF-DMA) by using in particular a Suzuki cross-coupling reaction between iodo-TTF and -dimethylaminophenylboronic acid and a TTF-vinyldimethylaniline (TTF-VDMA) by a Wittig-type condensation notably between TTF-carboxaldehyde and p-(dimethylamino)benzyltri-
phenylphosphonium bromide. Their NLO response, evaluated at 1.064 μm by the Hyper Raleigh Scattering technique, leads to β values around 240 × 10 -30 cm 5 esu -1 , in both cases. Additionally, these monomeric species are observed to exhibit very strong multiphoton fluorescence in solution after one electron oxidation. Different routes are discussed toward a possible engineering of TTF-donor based chromophores into oligomeric stacks in the solid state.
is related to the appearance of an extremely intense HOMO f LUMO-based low-lying transition, occurring at 1260 nm upon fractional oxidation, thus providing new and unexpected interest in TTF-donor substituted molecules. To illustrate the chemical feasibility of such species, two kinds of derivatives are synthesized: a TTF-dimethylaniline (TTF-DMA) by using in particular a Suzuki cross-coupling reaction between iodo-TTF and -dimethylaminophenylboronic acid and a TTF-vinyldimethylaniline (TTF-VDMA) by a Wittig-type condensation notably between TTF-carboxaldehyde and p-(dimethylamino)benzyltri-
phenylphosphonium bromide. Their NLO response, evaluated at 1.064 μm by the Hyper Raleigh Scattering technique, leads to β values around 240 × 10 -30 cm 5 esu -1 , in both cases. Additionally, these monomeric species are observed to exhibit very strong multiphoton fluorescence in solution after one electron oxidation. Different routes are discussed toward a possible engineering of TTF-donor based chromophores into oligomeric stacks in the solid state.
Information
| Item Type | Journal |
|---|---|
| Divisions |
» Laboratory for Terrestrial and Aquatic Ecosystems » Faculty of Science and Technology |
| ePrint ID | 212 |
| Date Deposited | 2014-12-14 |
| Further Information | Google Scholar |
| URI | https://univ-soukahras.dz/en/publication/article/212 |
BibTex
@article{uniusa212,
title={Quadratic Nonlinear Optical Response in Partially Charged Donor-Substituted Tetrathiafulvalene: From a Computational Investigation to a Rational Synthetic Feasibility},
author={Jean François Lamère, Isabelle Malfant, Alix Sournia-Saquet, Pascal G-Lacroix, Tahar ABBAZ, Abdel-Krim Gouasmia and Jean Marc Fabre, Lakhémici Kaboub},
journal={Chemistry of Materials}
year={2007},
volume={19},
number={4},
pages={805-815},
publisher={}
}
title={Quadratic Nonlinear Optical Response in Partially Charged Donor-Substituted Tetrathiafulvalene: From a Computational Investigation to a Rational Synthetic Feasibility},
author={Jean François Lamère, Isabelle Malfant, Alix Sournia-Saquet, Pascal G-Lacroix, Tahar ABBAZ, Abdel-Krim Gouasmia and Jean Marc Fabre, Lakhémici Kaboub},
journal={Chemistry of Materials}
year={2007},
volume={19},
number={4},
pages={805-815},
publisher={}
}