New molecular and polymeric frameworks via metal-ligand self-assembly and hydrogen-bonding

This thesis deals with the synthesis of hydrogen-bonded networks, molecular polygons and coordination networks using two different classes of nitrogen containing ligands and transition metal ions or complexes.; The first part of the thesis describes the use of 4,7-phenanthroline, 1, as a ligand in coordination chemistry. Coordinating 1 directly to transition metal ions, a series of coordination polymers and networks, 2--4, 6 and 7, were synthesized and their structural features studied. Utilizing 1 as a hydrogen-bond acceptor, a series of second-sphere hydrogen-bonded networks were synthesized, 9--14, and their structural features and thermal behaviour studied. Finally, a series of mixed first- and second-sphere coordination polymers 16--20 were synthesized employing 1 and their structural features and thermal behaviour studied.; The second part of the thesis involves the synthesis and characterization of discrete molecular polygons, coordination polymers, and networks with 2,2 '-bipyridine based ligands. These new ligands each possess external donor groups (pyridyl or cyano) or atoms (N) which were capable of extending the simple chelate complex resulting from 2,2'-bipyridine into a multi-metallic system; either by aggregation or polymerization.; When the substitution of the 2,2'-bipyridine unit was in the 5-position, three different polygons, 25--27 and 32, three polymers 28--29, 33, and a 2-D coordination network, 34, were synthesized and their structural features studied. When the chelate was substituted in the 6-position, two different of structures result, discrete molecular dimers, 38--40 and 42--47, and a coordination polymer, 41 . Finally, when substitution occurred in the 4-position, coordination polymers, 53--54, 2-D networks, 55 and 57, and a 3-D diamondoid network, 56, can be synthesized. Additionally, when the asymmetric version of the 4-substitiuted ligand was coordinated to an octahedral metal ion, fac- and mer-isomers 58--60 resulted. In the case of the Ru(II) complex, 60, these geometric isomers were separated by preparatory TLC and isolated.