Ag(I) containing supramolecular architectures with flexible asymmetric ligands

Abstract

This thesis describes the synthesis and characterization of a series of metallo-supramolecular complexes, synthesized with either 3,4 dipyridyl ketone (LK34), 3,4 dipyridyl ketone oxime (LO34) or 3,4-dipyridyl methanol (LA34) and different Ag(I) salts. Chapter one introduces supramolecular architectures, focusing on metallo-supramolecular chemistry and coordination polymers. The common motifs observed in this work are then defined, along with different supramolecular interactions. Chapter two discusses the ligand design, before detailing the synthesis and characterisation of LK34, LO34 and LA34. A protonation study of LK34, and deprotonation study of LO34 are both addressed. Chapter three covers the synthesis and characterisation of 11 new complexes. Complexes {(AgLK34)ClO4}∞ and {(AgLK34)BF4}∞ were isomorphous, forming 1-D chains. Complexes {AgLK34NO3}∞, {[Ag2(LK34)2](PF6)2.4MeCN}∞ and {[Ag(LK34)2]PF6}∞ were also present as a simple 1-D chains. Complexes {(AgLK34)2SiF6.3H2O.⅓MeCN}∞ and {(AgLK34)2SO4.3⅓H2O}∞ were also isomorphous, present as a side by side double helix. Complexes {AgLK34CF3CO2}∞ and {AgLK34CF3CF2CO2}∞ formed 2-D sheets, while (AgLK34CF3SO3)4 was present as discrete Ag4L4 squares. Finally, compound {(LK34+2H+)[PF6]2} contained no Ag(I) cations, instead the pyridine rings (Npy) of the ligand were protonated. Chapter four covers the synthesis and characterisation of nine new complexes. Compounds {[AgLA34]ClO4.½H2O}∞ and {[AgLA34]BF4.H2O}∞ were isomorphous, both present as a 1-D helix. Structure {AgLA34CF3CF2CO2}∞ also formed a helix, while structures {[AgLA34]PF6}∞ and {AgLA34CF3SO3}∞ formed double helices. Complex {AgLA34NO3}∞ formed a 1-D meso-helical chain. The complex {AgLA34CF3CF2CO2}∞ was present as a 2-D sheet comprised of helical chains. Finally, complexes (AgLA34CF3CO2)6 and (AgLA34CF3CF2CF2CO2)6 were also both isomorphous, present as discrete hexameric macrocycles. Chapter five covers the synthesis and characterisation of four new complexes. Complex {(AgLO34)ClO4.2MeOH}∞ formed a 1-D chain, while complexes {(AgLO34)BF4.2EtOH.H2O}∞, {(AgLO34)PF6}∞ and {(AgLO34CF3SO3).EtOH}∞ all form1-D meso-helical chains. Chapter six draws a comparison and contrast between the complexes formed, addressing the influence of both the functional group of the ligand as well as anion and solvent effects. A brief look at future work is all addressed. The appendix contains crystallographic tables for all compounds.