The studies presented in this thesis are in two areas. An investigation of aromatic nitrene molecules using EPR spectroscopy was undertaken. This revealed a general tendency for these molecules to exhibit two forms when trapped in a crystalline lattice. This is qualitatively interpreted as a perturbing effect of nitrogen evolved during generation from the azide. Single crystal experiments were made on 2,4,6-tribromophenyl nitrene, which exhibited an unusually large anisotropy in the zero field splitting, implying a bent structure. Temperature variation of several aromatic nitrene zero field splittings were made. The variation was interpreted as thermal averaging amongst states possessing different zero field parameters. The nature of these states however, could not be inferred. The variation is compared with similar studies. A computer program to least squares fit EPR angular data to a spin Hamiltonian has been written. This programme was used to obtain a description of the angularly dependent EPR data from an aromatic nitrene, and also for a radical species with a large hyperfine interaction. / Science, Faculty of / Chemistry, Department of / Graduate

Two phase transitions have been found in DEM(TCNQ)₂ at 400(3) K and at 442(6) K to 453(6) K using ESR and measurements of the microwave conductivity. These temperatures are less than the values of 415 K and 483 K previously obtained from temperature dependent Guinier measurements. Below 400(3) K two ESR lines, I and II are observed corresponding to the two stacks, B and A, in DEM(TCNQ)₂. Above 400(3) K and below 453(6) K only one line remains with the same g value as line I. The angular dependence of the g value was fitted to g[sub=‖]² = g[sub=⊥] ²cos2θ + g²sinθ and values of g[sub=⊥] = 2.003551(14) and g[sub=‖] = 2.00273015) were obtained. Between 298 K and 442(6) K the conductivity was that of a semiconductor with an exitation energy E[sub=0] = 0.385(52) e.v. The -4k[sub=⌐] phase transition is postulated at 447(9) K. The phase transition at 400(3) K is due to a transfer of spin density from stack A to stack B, and has no effect on the total spin susceptibility or on the conductivity to within the experimental error. / Science, Faculty of / Physics and Astronomy, Department of / Graduate

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published_or_final_version / Physics / Master / Master of Philosophy