Treatment of dichloromaleic anhydride and 1,8-diaminonaphthalene in either benzene or toluene under refluxing conditions gives low yields of the new heterocyclic compound 8,9-dichloropyrrolo[1,2-a]perimidin-10-one. This product has been isolated and characterized in solution by NMR, IR, and UV/vis spectroscopies, and the solid-state structure of 8,9-dichloropyrrolo[1,2-a]perimidin-10-one has been established by X-ray crystallography. The nature of the HOMO and LUMO levels of 8,9-dichloropyrrolo[1,2-a]perimidin-10-one has been studied by extended Hückel molecular orbital calculations.

This work is mainly concentrated on the development of new versatile ligand based on N,N’-disubstituted-1,8-diaminonaphthalene (1,8-DAN) for main group chemistry. Therefore, our initial efforts were made on the design of new ligand scaffold by using 1,8-DAN. Following that, new ligand family supported by 1,8-DAN was applied as ligands to main group elements (B, Al, In, Ga, and C). Furthermore, six-membered ring carbenes which are derived from the reaction between N,N’-disubstituted-1,8-diaminonaphthalene and carbon are also investigated. In addition, the stable carbenes were implied as a new ligand system for palladium, leading to the formation of metal ligand complexes. Therefore, the synthesis and reactivity of these complexes are also reported. Chapter I gives an explanation on the basic concepts in terms of the ligand designs and reports the reasons why N,N’-disubstituted-1,8-diaminonaphthalene has been chosen as the framework of for these ligands. Chapter II presents the approach to synthesize ligands depending on the substitution. Regarding this, three methods were successfully used: reductive amination, application of acyl halide followed by reduction, and copper catalyzed C-N coupling reactions. Chapter III describes the reactions between the N,N’-disubstituted-1,8-diaminonaphthalene and main group elements B, Al, Ga, and In in 13 group. In this chapter, a variety of mononuclear and dinuclear complexes are investigated and fully characterized. Furthermore, some computational studies are also reported for the comparison with experimental results. Chapter IV deals with new ligand family, carbene, which is derived from N,N’-disubstituted-1,8-diaminonaphthalene. Therefore, not only fundamental concepts for the NHC (N-heterocyclic carbene) are discussed but also synthetic pathways are introduced. Moreover, interesting features of free carbene are presented as well. Chapter V reports the potential of this new carbene ligand family as ligands for transition metal compound, especially, Pd(II) compounds. Several different pathways for synthesizing the desired metal carbene complexes are presented.

One of the main challenges to transform highly useful Direct Methanol Fuel Cells (DMFC) into a commercially viable technology has been to develop a low cost polymer electrolyte membrane (PEM) with high proton conductivity, high stability and low methanol crossover under operating conditions desirably including high temperatures. Nafion, the widely used PEM, fails to meet all of these criteria simultaneously. Recently developed acid-base polymer blend membranes constitute a promising class of PEMs alternative to Nafion on above criteria. Even though some of these membranes produce better performance than Nafion, they still present numerous opportunities for maximizing high temperature proton conductivity and dimensional stability with concomitant minimization of methanol crossover. Our contribution embarks on the fundamental study of one such novel class of blend membranes viz., sulfonated poly (ether ether ketone) (SPEEK)(95 % by weight) blended with polysulfone tethered with base (5 % by weight) such as 2-aminobenzimidazole (ABIm), 5-amino-benzotriazole (BTraz) and 1H-perimidine (PImd), developed by Manthiram group at The University of Texas at Austin. In this work, we report extensive all-atom classical as well as ab-initio molecular dynamics (MD) simulations of such water-methanol solvated blend membranes (as well as pure SPEEK and Nafion) the first time. Our approach consists of three steps: (1) Predict dynamical properties such as diffusivities of water, methanol and proton in such membranes (2) Validate against experiments (3) Develop understanding on the interplay between basic chemistry, structure and properties, the knowledge that can potentially be used to develop better candidate membranes. In particular, we elucidate the impact of simple, fundamental physiochemical features of the polymeric membranes such as hydrophilicity, hydrophobicity, structure or the size of the base on the structural manifestations on the bigger scale such as nanophase segregation, hydrogen bonding or pore sizes, which ultimately affect the permeant transport through such systems. / text