Title

The self-assembly of metallosupramolecular architectures.

Date of Award

1996

Degree Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

First Advisor

Loeb, Stephen,

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

This thesis describes the design, synthesis and characterization of metallosupramolecular cleft and box-shaped molecules. These compounds are generated via the self-assembly of building block compounds; metallated thioether complexes and aronatic N-donor ligands. Chapter Two describes the synthesis and characterization of the building block compounds. Cyclometallation of the thioether ligand 1,3-bis(phenylthio-methyl)benzene (PhS$\sb2$) with (Pd(CH$\sb3$CN)$\sb4$) (BF$\sb4\rbrack\sb2$ produced the species (Pd(PhS$\sb2$)(CH$\sb3$CN)) (BF$\sb4$). By varying the S-R group, a family of compounds were synthesized each possessing different physical properties. The metallated ligands exhibited inversion of sulfur and this was studied via variable temperature $\sp1$H NMR spectroscopy. As well, several ligands of the form 1,2,4,5-tetrakis-(phenylthiomethyl)benzene (PhS$\sb4$) were synthesized. These ligands underwent the cyclometallation reaction twice, forming the doubly palladated compound (Pd$\sb2$(PhS$\sb4$)(CH$\sb3$CN)$\sb2\rbrack$ (BF$\sb4\rbrack\sb2$, In an attempt to produce a trigonal bipyramidal Pd(II) complex with 1,10-phenanthroline, an uncommon square pyramidal geometry was produced. These building block compounds were characterized through the use of $\sp{13}$C$\{\sp1$H$\}$ and $\sp1$H NMR spectroscopy as well as X-ray crystallography. Chapter Three describes the synthesis of molecular clefts and boxes from the building block compounds developed in Chapter Two. When mixed in a ratio of 2:1, (Pd(PhS$\sb2$)(CH$\sb3$CN)) (BF$\sb4$):4,7-phenanthroline, the molecular cleft ((Pd(PhS$\sb2))\sb2$(4,7-phen)) (BF$\sb4\rbrack\sb2$ (Ph-Cleft) can be isolated in quantitative yields. This was found to be the case with the n-butyl version of the ligand as well. The self-assembly of a molecular box was achieved by the addition of (Pd$\sb2$(PhS$\sb4$)(CH$\sb3$CN)$\sb2$) (BF$\sb4\rbrack\sb2$ to 4,7-phenanthroline in a 1:1 ratio. The sole product of this reaction is the molecular box, a cyclic complex containing three wall units, (Pd$\sb2$(PhS$\sb4$)) (BF$\sb4\rbrack\sb2$ and three corner pieces; 4,7-phenanthroline. Similar results were obtained utilizing the (Pd$\sb2$(BuS$\sb4$)(CH$\sb3$CN)$\sb2$) (BF$\sb4\rbrack\sb2$ compound with 4,7-phenanthroline. These supramolecular species were characterized by $\sp1$H NMR and mass spectrometry as well as X-ray crystallography.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis1996 .H35. Source: Masters Abstracts International, Volume: 37-01, page: 0266. Adviser: Stephen Loeb. Thesis (M.Sc.)--University of Windsor (Canada), 1996.