Nonlinear Optical Properties and All Optical Switching of Curcumin Derivatives.

In this work OR1(E1,6E) -1,7-bis (4-propyloxy phenyl) hepta-1,6-diene-3,5 dione compound is synthesized. The compound has been characterized via computational technique by studying the molecule's electronic structures through calculating its HOMO and LUMO energies, and its band gap energy (EHOMO-ELUMO). The nonlinear refractive index (NLRI) of the solution of OR1 compound in DMF solvent is determined using diffraction patterns (DPs) which resulted when a continuous wave laser beam of wavelength 473 nm traversed the compound solution in a glass cell of 1 mm thickness. By counting the number of rings under maximum beam input power, the NLRI of value 10- 6 cm2/W resulted. The NLRI is calculated once more via the Z-scan technique and a value of 0.25 × 10- 7 cm2/W is obtained. The vertical convection current in the OR1 compound solution appears to be responsible for the asymmetries noticed in the DPs. The temporal variation of each DP is noticed together with the evolution of DPs against beam input power. DPs are numerically simulated based on the Fresnel-Kirchhoff integral with good accord compared to the experimental findings. Dynamic and static all-optical switching in the OR1 compound using two laser beams (473 and 532 nm) is tested successfully.

The nonlinear optical properties of two dihydropyridones derived from curcumin.

Two dihydropyridone compounds are synthesized from curcumin using microwave radiation. Both compounds were identified by their melting points and 1HNMR spectra. The nonlinear properties viz., nonlinear absorption coefficients and nonlinear refractive index of both compounds were calculated at wavelength 473 nm using the diffraction ring patterns and Z-scan techniques separately. The diffraction ring patterns evolved from circular symmetric to asymmetric due to convection current in the vertical direction. As a result of using Gaussian laser beam, the Fraunhofer approximation of the Fresnel-Kirchhoff diffraction, have led to successful simulation of the diffraction ring patterns with good quantitative and excellent qualitative agreements compared with experimental results. Optical limiting property has been tested in both compounds.

Strong intramolecular hydrogen bonds and steric effects involving C═S groups: An NMR and computational study.

A number of 5-acyl rhodanines and thiorhodanines with bulky acyl groups (pivaloyl and adamantoyl), not previously available, have been synthesized. The compounds are shown to exist in the enol form. Structures have been calculated using both the MP2 approach and the B3LYP-GD3BJ functional and the 6-311++G(d,p) basis set. Hydrogen bond energies are estimated by subtracting energies of a structure with the OH group turned 180° from those of the intramolecularly hydrogen-bonded one. Properties such as OH chemical shifts, two-bond isotope effects on 13 C chemical shifts, electron densities at the bond critical point from atoms in molecules analysis, and the hydrogen bond energies show that the sterically hindered compounds have stronger hydrogen bonds than methyl or isopropyl derivatives. The combination of oxygen and sulfur derivatives enables a detailed analysis of hydrogen bond energies.

Formation and temporal evolution of diffraction ring patterns in a newly prepared dihydropyridone.

A dihydropyridone has been prepared from butylamine and curcumin. A theoretical DFT study was conducted to determine the most stable conformer of the studied molecule (among three conformers) using the B3LYP/6-311+G(d,p) level of theory. This is assisted by the prediction of the 13C NMR chemical shifts of the conformers which then correlated with the observed 13C NMR chemical shifts. A TD-DFT study was conducted to analyze the electronic spectrum of the most stable conformer in order to determine the transitions responsible for the longer band in the electronic spectrum of the molecule. As well the frontier orbitals in the most stable conformer were analyzed to establish the density of donor and acceptor sites in the molecule that may be responsible for the nonlinear optical (NLO) properties of the studied molecule. Diffraction ring patterns were observed as a result of the use of visible, 473 nm, low power single mode laser beam traversed a thin cell containing solution of dihydropyridone. The nonlinear refractive index, n2, was determined based on the number of diffraction rings per a pattern observed and by the Z-scan technique and both results are compared. The upward convection heat effect appears to be responsible for the asymmetries observed in the diffraction ring patterns. The use of convergent and divergent laser beams has led to new types of diffraction ring patterns. Temporal evolution of each diffraction ring patterns was registered. The diffraction ring patterns experimentally obtained are numerically calculated using the Fresnel-Kirchhoff diffraction integral, with good qualitative and reasonable quantitative agreements.

NMR, MP2, and DFT study of thiophenoxyketenimines (o-thio-Schiff bases): Determination of the preferred form.

Five new thiophenoxyketinimines have been synthesized. 1 H and 13 C NMR spectra as well as deuterium isotope effects on 13 C chemical shifts are determined, and spectra are assigned. DFT and MP2 calculations of both structures, chemical shifts, and isotope effects on chemical shifts are done. The combined analysis reveals that the compounds are primarily on a zwitterionic form with an NH+ and a S- group and with a little of the neutral form mixed in. Very strong intramolecular hydrogen bonding is found and very high NH chemical shifts are observed. The theoretical calculations show that calculations at the MP2 level are best to obtain correct "C═S" chemical shifts.

Microwave-assisted synthesis of novel 2,3-dihydro-4-pyridinones.

Novel 2,3-dihydro-4-pyridinones were synthesized via the reaction of curcumin and primary amines or amine acetates under microwave irradiation. Montmorillonite K-10 was used as a catalyst. Reaction times did not exceed 120 s. The structures of the compounds were established by elemental analysis and from their mass, 1H- and 13C-NMR spectra.