The self-assembly of metallosupramolecular architectures.

Date of Award


Degree Type


Degree Name



Chemistry and Biochemistry

First Advisor

Loeb, Stephen,


Chemistry, Inorganic.




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.