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Isabelle Ledoux

Publications and source records attributed to Isabelle Ledoux.

12 recordsLinked to original sources
PubMed2006

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.

The synthesis and structural, photophysical, and second-order nonlinear optical (NLO) properties of a novel lanthanide terpyridyl-like complex family LLn(NO(3))(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 thoroughly 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 beta, 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.

Journal Article↗
PubMed2006

Motor unit conduction velocity distribution estimation from evoked motor responses.

Action potentials travel along the muscle fibers with a specific conduction velocity that depends on their structural and functional properties. Only the estimation of muscle conduction velocity distribution (MCVD) may be able to depict this propagation heterogeneity. Based on the method proposed by Cummins et al. (Electroenceph Clin Neurophysiol, 46:647-658, 1979) to estimate nerve conduction velocity distribution (NCVD), the present paper proposes a method that modifies the Cummins' approach to make it suitable for MCVD estimation from electrically evoked motor responses. The MCVD estimation algorithm was first assessed by means of simulated signals in order to control all signal features during the optimization process. Simulations showed that estimated distributions were very close to the true ones when taking into account the specificities of the muscle action potential, due to its generation and extinction (MSE divided by 5 on distribution standard deviation). This method was then applied to real signals. Elicited motor responses were recorded on the biceps brachii of healthy subjects either during repeated maximal stimulations at 20 Hz or during increasing intensity stimulations at 1 Hz. MCVD estimates were used to analyze fatigue and motor unit recruitment processes, respectively.

Action Potentials↗
PubMed2005

Lanthanide complexes for second order nonlinear optics: evidence for the direct contribution of f electrons to the quadratic hyperpolarizability.

This study descibes for the first time the nonlinear optical (NLO) properties of multipolar lanthanide complexes, Na3[Ln(dipic)3]. The "metal-induced" NLO activity enhancement is confirmed as a general property of f-block elements, and the direct participation of f electrons to the hyperpolarizability beta is strongly supported by experimental data.

Journal Article↗
PubMed2005

Structural modulation of the dipolar-octupolar contributions to the NLO response in subphthalocyanines.

Second order nonlinear optical properties of a series of trinitrosubphthalocyanine (SubPc) isomers were studied experimentally by electric field induced second harmonic (EFISH) generation and hyper Rayleigh scattering (HRS). These experimental values were compared to the ones obtained theoretically employing both sum over states (SOS) and finite field (FF) methods. From these studies, it was shown that the dipolar contributions to the beta tensor are very much dependent on the substitution pattern at the periphery of the subphthalocyanine macrocycle, whereas the octupolar contributions remain mostly unchanged. Consequently, it was deduced that SubPc is extremely well suited for the decoupling of octupolar and dipolar contribution to the NLO response.

Journal Article↗
PubMed2004

Synthesis, linear, and quadratic-nonlinear optical properties of octupolar D3 and D2d bipyridyl metal complexes.

A series of D3 (Fe(II), Ru(II), Zn(II), Hg(II)) and D2d (Cu(I), Ag(I), Zn(II)) octupolar metal complexes featuring different functionalized bipyridyl ligands has been synthesized, and their thermal, linear (absorption and emission), and nonlinear optical (NLO) properties were determined. Their quadratic NLO susceptibilities were determined by harmonic light scattering at 1.91 microm, and the molecular hyperpolarizability (beta0) values are in the range of 200-657 x 10(-30) esu for octahedral complexes and 70-157 x 10(-30) esu for tetrahedral complexes. The octahedral zinc(II) complex 1 e, which contains a 4,4'-oligophenylenevinylene-functionalized 2,2'-bipyridine, exhibits the highest quadratic hyperpolarizability ever reported for an octupolar derivative (lambdamax=482 nm, beta1.91(1 e)=870 x 10(-30) esu, beta0(1 e)=657 x 10(-30) esu). Herein, we demonstrate that the optical and nonlinear optical (NLO) properties are strongly influenced by the symmetry of the complexes, the nature of the ligands (donor endgroups and pi linkers), and the nature of the metallic centers. For example, the length of the pi-conjugated backbone, the Lewis acidity of the metal ion, and the increase of ligand-to-metal ratio result in a substantial enhancement of beta. The contribution of the metal-to-ligand (MLCT) transition to the molecular hyperpolarizability is also discussed with respect to octahedral d6 complexes (M=Fe, Ru).

2,2'-Dipyridyl↗
PubMed2004

All-optical orientation of photoisomerizable octupolar zinc(II) complexes in polymer films.

A new type of 4,4'-bis(styryl)-2,2'-bipyridine functionalized by a dialkylamino-azobenzene group has been prepared. This ligand has allowed the preparation of photoisomerizable octupolar tris(bipyridyl)zinc(II) complexes and the corresponding star-shaped polymer by atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). The photoisomerization properties of such new metallo-chromophores have been studied. The macroscopic molecular orientation of the corresponding doped and grafted NLO-polymer films is reported for the first time.

Journal Article↗
PubMed2003

Improved transparency--nonlinearity trade-off with boroxine-based octupolar molecules.

A series of octupolar molecules derived from the boroxine framework were designed and their optical nonlinearities were investigated by performing harmonic light scattering experiments in solution; the molecules were found to combine excellent transparency in the near UV-visible region (lambdamax < or = 280 nm) and significant first-order hyperpolarisabilities (up to beta(0) = 56 x 10(-30) esu).

Journal Article↗
PubMed2003

Synthesis, photophysical and nonlinear optical properties of macromolecular architectures featuring octupolar tris(bipyridine) ruthenium(II) moieties: evidence for a supramolecular self-ordering in a dentritic structure.

The synthesis, photophysical and nonlinear optical properties of several new multi-octupolar tris(bipyridine) ruthenium complexes are reported. The preparation on these complexes is based on the initial construction of multipodal 4,4'-dialkylaminostyryl-2,2'-bipyridine ligands (DAAS-bpy). Thermally stable polyimides featuring octupolar ruthenium trisbipyridyl complexes have been readily obtained by a polycondensation reaction. The controlled coordination strategy of dipodal and tripodal bipyridines to ruthenium(II) has also been successfully used to build bimetallic, trimetallic as well as the first metallodendrimer made of seven metallo-octupoles. These polymetallic species exhibit very intense absorption bands in the visible and long-lived luminescence. The quadratic NLO-susceptibilities beta of these macromolecules have been characterized by harmonic light scattering at 1.91 microm and compared with those of the corresponding monometallic species. The NLO studies clearly demonstrates a quasi-supramolecular ordering in the metallodendrimer.

Journal Article↗
PubMed2002

Three-dimensional nonlinear optical chromophores based on through-space delocalization.

Six permutations of 4-fold donor and/or acceptor substitution of paracyclophane at the 4, 7, 12, and 15 positions were synthesized to probe the phenomenon of three-dimensional delocalization on the nonlinear optical properties of organic materials. The interplay between through-bond intramolecular charge transfer (ICT) as well as three-dimensional, or through-space, ICT processes gives rise to large quadratic hyperpolarizability values. The determination of dipolar (beta(J)(=1)) and octupolar (beta(J)(=3)) irreducible tensor contributions to the overall beta tensor value is made possible by the polarized harmonic light scattering technique at 1.32 microm. The electric field-induced second-harmonic generation technique was also used at 1.91 microm for comparison. Significant experimental beta values for members of the series made of two centrosymmetric benzene-like units are a clear signature of a purely through-space ICT between two aryl subunits. The two configurational isomers that pair two dipolar donor-acceptor chromophores also exhibit octupolar character. Analysis of these two with an additive model for beta(J)(=1) and beta(J)(=3) reveals a strong three-dimensional inter-ring charge transfer.

Journal Article↗
PubMed2002

Zinc(II) as a versatile template for the design of dipolar and octupolar NLO-phores.

Thermally stable dipolar and octupolar (D2d, D3) NLO-phores are readily accessible by combining one, two, or three 4,4'-bis(dialkylaminostyryl)-[2,2']-bipyridyl ligands with zinc(II) salts. The off-resonant beta0 values point out the superiority of octupoles versus dipoles in terms of nonlinearity/transparency tradeoff. The octahedral tris(bipyridyl)zinc(II) complex exhibits a very large beta0 value (241 x 10-30 esu), which is the largest ever reported for octupolar molecules.

Journal Article↗