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Title: Quadratic nonlinear optical response in partially charged donor-substituted tetrathiafulvalene: From a computational investigation to a rational synthetic feasibility
Authors: Lamere, J. F ×
Malfant, I
Sournia-Sacquet, A
Lacroix, P. G
Fabre, Jean Marc
Kaboub, Lakhemici
Abbaz, Tahar
Gouasmia, Abdel-Krim
Asselberghs, Inge
Clays, Koen #
Issue Date: Feb-2007
Publisher: American Chemical Society
Series Title: Chemistry of Materials vol:19 issue:4 pages:805-815
Abstract: A computational (ZINDO) investigation is employed to estimate the molecular hyperpolarizability (beta) of a [(TTF-NH2)(8)] (TTF = tetrathiafulvalene) octameric stack at various fractional (0 < rho < 1) oxidation states of TTF rho+. While the neutral [(TTF-NH2)(8)] octamer exhibits a modest (7.6 x 10(-30) cm(5) esu(-1)) static beta(0) value, in relation to a nearly centrosymmetric electronic structure, the formal (TTF-NH2)(0.25+) oxidation state leads to a giant (beta(0) = 3891 x 10(-30) cm(5) esu(-1) per octamer) NLO response. This effect is related to the appearance of an extremely intense HOMO -> 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 p-dimethylaminophenylboronic acid and a TTF-vinyldimethylaniline (TTF-VDMA) by a Wittig-type condensation notably between TTF-carboxaldehyde and p-(dimethylamino)benzyltriphenylphosphonium bromide. Their NLO response, evaluated at 1.064 mu m by the Hyper Raleigh Scattering technique, leads to beta values around 240 x 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.
ISSN: 0897-4756
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Molecular Imaging and Photonics
× corresponding author
# (joint) last author

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