28.10.2015
Doctoral Dissertation

Dissertation: 13.11. FM Pia Bonakdarzadeh (Faculty of Mathematics and Science, Organic Chemistry)

Pia BonakdarzadehFM Pia Bonakdarzadeh defends her doctoral dissertation in Organic Chemistry "Supramolecular Coordination Polyhedra Based on Achiral and Chiral Pyridyl Ligands: Design, Preparation and Characterization”. Opponent Professor Jonathan W. Steed (University of Durham, UK) and custos Professor Kari Rissanen (University of Jyväskylä). The doctoral dissertation is held in English.

The thesis is based on design, preparation, and characterization of supramolecular coordination polyhedra. Directed by the ligand bend angle, complexation of the ligand and metal with predetermined coordination number and geometry resulted in variously shaped polyhedra. These large Pd3L6, Pd6L4, Pt6L4, Pd6L12, Pd12L24, Pd24L48, and Fe4L4 polyhedra are derived from eight purposely designed pyridyl ligands. Complexing bis(pyridyl) ligands with pyrrole, amine, carbazole, and imine as the ligand core with square-planar Pd2+ resulted in roughly spherical Pd6L12, Pd12L24, and Pd24L48 assemblies. Electron-rich and -deficient octahedral Pd6L4 and Pt6L4 cages were prepared from electron-deficient fluorine- and electron-rich methoxy-cored tris(pyridyl) ligands and cis-blocked Pd2+ or Pt2+. The size of these M6L4 cages were studied in solution, gas-phase and solid-state. Achiral electron-deficient fluorine-cored tris(bipyridyl) ligand and octahedral Fe2+ formed a racemic mixture of homochiral T-symmetric tetrahedral Fe4L4 cages, which upon crystallization from methanol resulted in spontaneous resolution. And lastly, an inherently chiral non-symmetrical bile acid-based ligand was used in self-assembly of hexameric Pd3L6, which could be easily transformed into trimeric Pd3L3Cl6 by addition of Cl and quantitatively reconstructed by subsequent addition of Ag+. All polyhedra prepared were thoroughly characterized by NMR (1H, 13C, 31P, 19F, 1H DOSY) and MS-analysis (ESI-MS, IM-MS). Additionally, six crystal structures were obtained.