Synthesis and Coordination of the Arylazo Ligands 1-(2-pyridylazo)-2-phenanthrol and 1-(8-quinolynazo)-2-phenanthrol

Abstract

The use of ligands 1-(2-pyridylazo)-2-phenanthrol and 1-(8-quinolinazo)-2-phenanthrol has afforded twelve new complexes that feature many different structural, mag- netic, and electronic properties. Chapter one deals with the aspects of materials chemistry which are pertinent to the material presented in this thesis. This includes inorganic chemistry, mag- netism, luminescence, and redox active ligands. The second chapter includes the experimental details of all the complexes and ligands presented herein. The main body of this work has been split into three parts. The first part presented in chap- ter three includes complexes of 1-(2-pyridylazo)-2-phenanthrol with the following transition metals [V(V), Cu(II), Co(II), Ru(II), Fe(II) and Fe(III)]. Of particular interest in this chapter is the Co(II) complex which exhibits thermal spin-crossover, and the Fe(II) complexes which offer interesting structural properties including a structural phase transition. The second part (chapter four) examines three lanthanide complexes (Gd, Tb, and Dy) with the ligand 1-(2-pyridylazo)-2-phenanthrol. These complexes feature intense absorptions in the visible region which results in these complexes having dye-like properties. Of particular note is the luminescence studies performed on these complexes. The final part (chapter five) of the work presented examines the synthesis and characterization of the ligand 1-(8-quinolinazo)-2-phenanthrol, and it’s coordina- tion chemistry (Fe(II), and Co(III)). The ligand offers quasi-reversible ligand cen- tered reductions at low potentials, which should offer the first step in the synthesis of valence-tautomer or charge-transfer complexes.