Part I. Design and realization of dipole parallel -aligned crystal lattices. Part II. Deamination of guanine and the hydrolysis of heterocumulenes

Part I of this dissertation deals with the crystal packing of symmetric and asymmetric acetophenone azines. These azines have the general formula X--Ph--C(Me)=N--N=C(Me)--Ph--Y, and they are called symmetric if X = Y and asymmetric if X ≠ Y. Our interest in these molecules stems from their ability to form dipole parallel-aligned crystals. The design of highly polar materials is important for numerous optical and electrical properties. For instance, a macroscopic dipole moment is essential for nonlinear optical (NLO) activity and this has important implications for information technologies. Chapters 1 and 2 discuss the design concepts involved in preparing dipole parallel-aligned crystals along with the preparation and crystallization of numerous different materials. Chapters 3--5 discuss the properties of the molecules introduced in the first two Chapters.;Part II of this dissertation discusses the deamination of guanine and the hydrolysis of heterocumulenes. Previous studies in our group of guaninediazonium ion in the absence of cytosine revealed that N1-C6 pyrimidine ring-opening occurs upon loss of N2. In Chapter 6 the thermodynamics and kinetics of the dediazoniation of guaninediazonium ion in the presence of cytosine are discussed. Our studies show that the hydrolysis of carbodiimide may be an important factor in the dediazoniation of guaninediazonium ion. Thus, we studied the addition of water to carbodiimide and we extended the investigation to include the hydrolysis of carbon dioxide. The results of our investigations of the hydrolyses of carbodiimide and carbon dioxide are reported in Chapter 7. Nucleophilic attack of water, or any nucleophile, on carbodiimide and carbon dioxide is guided in part by the quadrupole moments and electric dipole polarizability of C(NH)2 and CO2 and these values are reported and discussed in Chapter 8.