RESUMEN
Nine nonlinear optical (NLO) chromophores with pyridinium electron acceptors have been synthesized by complexing new proligands with {Ru(II)(NH(3))(5)}(2+) electron-donor centers. The presence of long alkyl/fluoroalkyl chain substituents imparts amphiphilic properties, and these cationic complexes have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Each complex shows three reversible/quasireversible redox processes; a Ru(III/II) oxidation and two ligand-based reductions. The energies of the intense visible d â π* metal-to-ligand charge-transfer (MLCT) absorptions correlate to some extent with the ligand reduction potentials. (1)H NMR spectroscopy also provides insights into the relative electron-withdrawing strengths of the new ligands. Single crystal X-ray structures have been determined for two of the proligand salts and one complex salt, [Ru(II)(NH(3))(5)(4-C(16)H(33)PhQ(+))]Cl(3)·3.25H(2)O (PhQ(+) = N-phenyl-4,4'-bipyridinium), showing centrosymmetric packing structures in each case. The PF(6)(-) analogue of the latter complex has been used to deposit reproducibly high-quality, multilayered Langmuir-Blodgett (LB) thin films. These films show a strong second harmonic generation (SHG) response from a 1064 nm laser; their MLCT absorbance increases linearly with the number of layers (N) and I(2ω)/I(ω)(2) (I(2ω) = intensity at 532 nm; I(ω) = intensity at 1064 nm) scales quadratically with N, consistent with homogeneous deposition. LB films on indium tin oxide (ITO)-coated glass show electrochemically induced switching of the SHG response, with a decrease in activity of about 50% on Ru(II) â Ru(III) oxidation. This effect is reversible, but reproducible over only a few cycles before the signal from the Ru(II) species diminishes. This work extrapolates our original solution studies (Coe, B. J. et al. Angew. Chem., Int. Ed.1999, 38, 366) to the first demonstration of redox-switching of NLO activity in a molecular material.
Asunto(s)
Complejos de Coordinación/síntesis química , Rutenio/química , Tensoactivos/síntesis química , Complejos de Coordinación/análisis , Cristalografía por Rayos X , Electroquímica , Electrones , Ligandos , Espectroscopía de Resonancia Magnética , Modelos Moleculares , Estructura Molecular , Fenómenos Ópticos , Oxidación-Reducción , Sales (Química)/química , Estereoisomerismo , Tensoactivos/análisisRESUMEN
We measured the second harmonic generation response of a thin film consisting of chiral molecules with four wave plates having different retardation coefficients. By means of the fitting procedure described in a previously reported formalism, we demonstrated that a single set of tensor components of second order surface nonlinearities fits all the data. Our results provide clear experimental evidence for the validity of this method, which can find applications in the studies of chiral structures and achiral anisotropic materials.
RESUMEN
Chiral spectroscopic study: The intensities of second harmonic generation chiral spectroscopy are obtained from the dispersion of the nonlinear optical susceptibility components, as a function of wavelength for helicenbisquinone thin films (see figure). A single formalism fits all the data simultaneously, and the findings constitute an important milestone towards the development of a new experimental technique.