Syntheses and quadratic optical nonlinearities of ruthenium(II) complexes with ethynyl-connected N-methylpyridinium electron acceptors

We have prepared a number of new dipolar complexes containing ethynyl or buta-1,3-diynyl units linking electron-rich {Ru(II)(NH3)5}2+, trans-{Ru(II)(NH3)4L}+ (L = pyridine or N-methylimidazole), or trans-{Ru(II)Cl(pdma)2}+ [pdma = 1,2-phenylenebis(dimethylarsine)] centers to pyridinium electron acceptors. In acetonitrile solutions at 295 K, the new complexes display unusual blue-shifting of their metal-to-ligand charge-transfer (MLCT) bands as the conjugation is extended, in a fashion similar to that of the corresponding ethenyl systems. Hyper-Rayleigh scattering (HRS) and Stark spectroscopic measurements provide direct and indirect estimates of static first hyperpolarizabilities beta0, and both the linear and nonlinear optical (NLO) properties are temperature- and medium-dependent. Thus, at 77 K in butyronitrile glasses, the MLCT bands display more normal red shifts upon conjugation extension. While the Stark-derived beta0 values generally increase as n (the number of ethynyl units) increases from 0 to 2, the HRS data show maximization at n = 1 for two of the ammine series but an increase upon moving from n = 1 to 2 for the pdma complexes. Comparisons with the analogous ethenyl chromophores show that the latter generally display larger beta0 values, whether determined via HRS or Stark data, and the inferiority of the ethynyl systems in terms of NLO response is more pronounced when n = 2. This differing behavior is attributable primarily to larger increases in the transition dipole moment mu12 (and, hence, donor-acceptor pi-electronic coupling) on elongation in the ethenyl chromophores.     

Syntheses and properties of two-dimensional, dicationic nonlinear optical chromophores based on pyrazinyl cores

Six new dicationic 2D nonlinear optical (NLO) chromophores with pyrazinyl-pyridinium electron acceptors have been synthesized by nucleophilic substitutions of 2,6-dichloropyrazine with pyridyl derivatives. These compounds have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. Large red shifts in the intense, π → π* intramolecular charge-transfer (ICT) transitions on replacing -OMe with -NMe(2) substituents arise from the stronger π-electron donor ability of the latter. Each compound shows a number of redox processes which are largely irreversible. Single crystal X-ray structures have been determined for five salts, including two nitrates, all of which adopt centrosymmetric packing arrangements. Molecular first hyperpolarizabilities β have been determined by using femtosecond hyper-Rayleigh scattering at 880 and 800 nm, and depolarization studies show that the NLO responses of the symmetric species are strongly 2D, with dominant "off-diagonal" β(zyy) components. Stark (electroabsorption) spectroscopic measurements on the ICT bands afford estimated static first hyperpolarizabilities β(0). The directly and indirectly derived β values are large, and the Stark-derived β(0) response for one of the new salts is several times greater than that determined for (E)-4'-(dimethylamino)-N-methyl-4-stilbazolium hexafluorophosphate. These Stark spectroscopic studies also permit quantitative comparisons with related 2D, binuclear Ru(II) ammine complex salts.     

Quadratic and cubic nonlinear optical properties of salts of diquat-based chromophores with diphenylamino substituents

A series of chromophoric salts has been prepared in which 4-(diphenylamino)phenyl (Dpap) electron donor groups are connected to electron-accepting diquaternized 2,2'-bipyridyl (diquat) units. The main aim is to combine large quadratic and cubic nonlinear optical (NLO) effects in potentially redox-switchable molecules with 2D structures. The chromophores have been characterized as their PF(6)(-) salts by using various techniques including electronic absorption spectroscopy and cyclic voltammetry. The visible absorption spectra are dominated by intense π → π* intramolecular charge-transfer (ICT) bands, and all of the compounds show two reversible or quasireversible diquat-based reductions and partially reversible Dpap oxidations. Single crystal X-ray structures have been obtained for one salt and for the precursor compound (E)-4-(diphenylamino)cinnamaldehyde, both of which adopt centrosymmetric space groups. First hyperpolarizabilities β have been measured by using hyper-Rayleigh scattering (HRS) with a 800 nm laser, and Stark (electroabsorption) spectroscopy of the ICT bands affords estimated static first hyperpolarizabilities β(0). The directly and indirectly derived β values are large and generally increased substantially for the bis-Dpap derivatives when compared with their monosubstituted analogues. Polarized HRS studies show that the NLO responses of the disubstituted species are dominated by "off-diagonal" β(zyy) components. Lengthening the diquaternizing alkyl unit lowers the electron-acceptor strength and therefore increases the ICT energies and decreases the E(1/2) values for diquat reduction. However, compensating increases in the ICT intensity prevent significant decreases in the Stark-based β(0) responses. Cubic NLO properties have been measured by using the Z-scan technique over a wavelength range of 520-1600 nm, revealing relatively high two-photon absorption cross-sections of up to 730 GM at 620 nm for one of the disubstituted chromophores.     

Quantum Mechanics from Symmetry and Statistical Modeling

Quantum theory is derived from a set ofplausible assumptions related to the following generalsetting: For a given system there is a set ofexperiments that can be performed, and for each suchexperiment an ordinary statistical model is defined. Theparameters of the single experiments are functions of ahyperparameter which defines the state of the system.There is a symmetry group acting on the hyperparameters, and for the induced action on the parameters ofthe single experiment a simple consistency property isassumed, called permissibility of the parametricfunction. The other assumptions needed are rather weak. The derivation relies partly on quantumlogic, partly on a group representation of thehyperparameter group, where the invariant spaces areshown to be in 1-1 correspondence with the equivalenceclasses of permissible parametric functions. Planck'sconstant only plays a role connected to generators ofunitary group representations.     

Synthesis and debenzoylation products of two perbenzoylated 2-substituted 5-D-galactosyl-1,3,4-oxadiazoles

The synthesis of 2-(p-chlorophenyl)-5-[1′,2′,3′,4′,5′-penta-O-benzoyl-D-galactopentitol-1-yl]-1,3,4-oxadiazole is described. Its debenzoylation gave an equilibrium mixture of the 1,3,4-oxadiazole derivative without protection of the hydroxyl group and the N-benzoyl-D-galactono-1,4-lactonehydrazone. A similar equilibrium was observed by debenzoylation of 2-phenyl-5-[1′,2′,3′,4′,5′-penta-O-benzoyl-D-galactopentitol-1-yl]-1,3,4-oxadiazole. The ¹H, ¹³C nmr and ms spectra of these compounds are presented.     

Temperature‐Programmed Packed Capillary Liquid Chromatography Coupled to Fourier‐Transform Infrared Spectroscopy

Temperature‐programmed packed capillary liquid chromatography has been coupled off‐line to Fourier‐transform infrared spectroscopy, utilizing a commercially available interface with a pneumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to non‐aqueous reversed phase separations of polymer additives, resulting in constructed Gram‐Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in‐house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature‐programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P‐EPQ.     

Efficient,Reversible Redox‐Switching of Molecular First Hyperpolarizabilities in Ruthenium(II) Complexes Possessing Large Quadratic Optical Nonlinearities

Low‐energy metal‐to‐ligand charge‐transfer (MLCT) excitations are associated with the very large molecular nonlinear optical (NLO) coefficients, β, of the complexes [Ru^II(NH₃)₅(N‐R‐4,4′‐bipyridinium)]³⁺ (R=methyl, phenyl, or 4‐acetylphenyl). Chemical oxidation to the Ru^III forms causes bleaching of the MLCT absorptions and marked attenuation of the NLO responses. Both effects are completely reversed upon re‐reduction, and the extent of the β switching is about 10‐ to 20‐fold.     

Elastic recovery of immiscible blends Part 2: Transient flow histories

Immiscible polymer blends are known to display an unusual elastic recovery after stress release. Recoil after steady-state shearing is well understood and obeys specific scaling relations. Releasing the stress before the steady-state morphology has been reached results in a more complex elastic recovery, including very large final values. This behaviour is investigated systematically. Model blends are used, consisting of nearly inelastic components; hence the measured recoil can be attributed totally to contributions from the interface. The instantaneous structure at the onset of the recoil can vary greatly in transient experiments, ranging from slightly deformed droplets to highly elongated filaments. The effects of this initial structure on the ultimate recoil and time scale of the recovery are studied. The morphological changes during recovery are considered as well. It is demonstrated that they can be computed from the normal stresses during stress relaxation with comparable initial morphologies. This indicates that the same morphological changes occur during stress relaxation and constrained recoil. A scaling relation for the recoil curves has been derived from the Doi-Ohta theory, which is confirmed by the experiments. Received: 9 December 1998 Accepted: 5 April 1999     

Light-induced multi-wavelength lasing in dye-doped chiral nematic liquid crystals due to strong pumping illumination

The influence of the pump laser beam on the lasing spectral characteristics in dye-doped cholesteric liquid crystal is investigated. Under the influence of the pump laser pulses with different repetition rates and energies, non-linear reorientation and light-induced flow reorientation of chiral nematic liquid crystals (CLC) molecules was observed. Independent of the reorientation mechanism, multi-wavelength lasing was achieved due to stepwise uncoiling of the CLC structure. Under the influence of a pump laser beam with low repetition rate, Cano–Grandjean disclination defect lines were induced which remain even after removal of the laser beam.