Hydrothermal synthesis of metal coordination polymers using mixed pyridine-carboxylate ligands

Zeolites are an important class of natural and synthetic microporous solids made of aluminosilicate building blocks. They have commercial importance in the fields of selective sorption and separation of gases, cation-exchange and catalysis. Their properties result from the chemical functionality, high internal surface area and crystalline regularity of their micropores. In order to extend these properties and applications, synthesis of new zeolite analogue materials, or zeotypes, has been an active area for the past 20 years. Recently zeotypes constructed from crystalline metal-organic framework polymers (MOFs) have been prepared by our group and others that offer quite complementary properties to purely inorganic oxide framework zeotypes. Chapter 1 surveys the background to their successful design and preparation. Typically the organic components of the MOFs may be from pyridyl N-donor ligands, or carboxylate O-donor ligands. Many metals prefer mixed N, O-ligand donor sets. In this thesis we will explore the chemistry behind construction of MOFs from ligands that possess both pyridine and carboxylate functionality together.; Chapter 2 explores the MOFs formed from copper, a labile and versatile metal, with the simplest archetypal ligand of this class, pyridine-4-carboxyl ate or isonicotinate [INA]. Chapter 3 explores metal-ligand systems with slight additional complexity, the pyridine dicarboxylates [PDAs], with Zn, Cd, Ni, Co and Cu metals.; Chapter 4 looks at MOFs formed from extended two ring systems, the bipyridine dicarboxylates [BDAs] with lanthanide metals. Finally in Chapter 5 we explore the synthesis of tris-chelated [M(BDA)3] species for M = Ru with the idea to prepare thermally stable chiral building blocks for enantiopure MOFs.; In conclusion pyridine-carboxylates offer a wide range of possibilities for MOF zeotype formation. The present work shows some of the scope for architectural design and manipulation with the caveat that reaction conditions may have a profound effect on the product outcome. The hydrothermal technique is shown to be highly successful and adaptable to MOF formation for many metal and ligand systems. Judicious use of conditions may also allow partial hydrolysis to form hybrid solids incorporating both organic ligand and metal hydroxides. The physico-chemical properties of these may in many cases prove superior to pure MOFs. (Abstract shortened by UMI.)...