Stereoselectivity in Reactions of Metal Complexes. Part XIV.. Use of circular dichroism to determine the stereoselective formation of [M(his)2] and [M(PhEt-sal)2] (M = Ni2+, Cu2+, his = histidine,PhEt-sal = N-(1-phenylethyl)salicylaldimine)

The stereoselective formation of the 1:2 complexes [M(his)₂] and [M(PhEt-sal)₂] (M = Ni²⁺, Cu²⁺, PhEt-sal = N-(1-phenylethyl)salicylaldimine) has been determined by circular dichroism (CD) measurements. Stereoselectivity, defined as S = K_meso/2K_rac' has been found to be 2.48 for [Ni(his)₂], corresponding to a 21% excess of the mixed species relative to the statistical amount. This value is temperature-independent between 15 and 35°. Whereas the absence of stereoselectivity in the formation of [Cu(prol)₂] is confirmed, weak stereoselectivity is observed for [Cu(his)₂] (2% excess of the mixed species). The CD intensity of the latter complex strongly depends on temperature and decreases by 12%, when the temperature is increased from 15 to 35°. Small but significant stereoselectivity is found for the formation of the Schiff-base complexes [Ni(PhEt-sal)₂] and [Cu(PhEt-sal)₂] in acetone with 1.0% and 2.4% excess, respectively, of the mixed species over the statistical value.     

A molecular simulation study of a cyclic siloxane with attached biphehylyl 4-allyloxybenzoate mesogens

A molecular simulation study of a cyclic siloxane macromolecule based on a pentamethylcyclosiloxane core and biphenylyl 4-allyloxybenzoate mesogenic units is reported. Molecular dynamics and semi-empirical calculations were used to provide insight into the conformation and the dielectric properties of the material. Out of three proposed conformations of the molecules, a cylindrical conformation was found to be the most probable. The intermolecular interactions were found to be optimized for the case where the mesogenic groups were planar and parallel to each other. The calculated mesogen length and inter-mesogen distances were consistent with available X-ray data. Electrostatic interactions were found to make a very significant contribution to the total energy. For the cylindrical model, the major component of the dipole was calculated to be along the long axis of the molecules. This is consistent with the alignment of the molecules parallel to a low frequency applied electric field as found experimentally.     

Analysis of electromagnetic radiation from shaped-end radiatorsusing the finite difference time domain method

The finite difference time domain (FDTD) technique is a popular method for analyzing electromagnetic scattering, radiation, and penetration problems. Several authors have recently applied the FDTD method to antenna radiation problems. To date, the antenna structures considered have been wire and conical monopole antennas, rectangular waveguides, pyramidal horn antennas, and microstrip antennas. Results from these analysis have been in the form of normalized field patterns and no results showing absolute gain have been presented. The article demonstrates the first staircased application of the FDTD method to the analysis of radiation from circular waveguides and other shaped-end radiators. Results of absolute gain versus angle are shown for a straight-cut circular waveguide and for two different shaped-end radiators. All FDTD analyses are full three-dimensional computations and are compared in each case with measured data