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Title: Complexes of tripodal and macrocyclic Schiff base ligands
Author: Archibald, Stephen James
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 1995
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The synthesis, structures and physical properties of tripodal and macrocyclic Schiff base ligands and their complexes are described. All ligands are synthesised by the condensation of amines with 2,6-diformyl- or 2,6-diacetyl-phenols. The synthesis of a novel dodecadentate tripodal Schiff base ligand, L1H3, is described. Reaction of L1H3 with Ln(ClO4)3 where Ln=La, Pr gives complexes of the form [Ln(L1H3)(H2O)](CIO4)3 and where Ln=Y, [Y(L1H3)](CIO4)3. The single crystal X-ray structures of L1H3 and complexes are described. L1H3 reacts with Gd(CIO4)3 in the presence of Cu(CIO4)2 and N,N-diisopropyl-ethylamine resulting in hydrolysis of the acetal functionality to give a complex of the nonadentate tripodal ligand L5H3, [Gd(L5H3)(H2O)2](CIO4)3, the single crystal X-ray structure of which is described. A similar reaction occurs with Ni(CIO4)2, giving [Ni(L5H3)](CIO4)2, The X-ray structure of which is also described. The preparation of L-H3, a related tripodal nonadentate ligand, is described and the structure determined by single crystal X-ray analysis. Complexes prepared by reaction with M(CIO4)2, M=Ni, Zn, are of the form [M(L2H3)](CIO4)2 and the single crystal X-ray structures show the two complexes are isostructural. The Schiff base macrocycle [L3H4](PF6)2 reacts to form [Cu2L3(CH3CO2)]Br preferentially in the presence of La(CIO4)3 and Cu(CH3CO2)2. The single crystal X-ray structure is described. A template condensation of 2,6-diformyl-4-methylphenol and tris(2-amino-ethyl)amine around yttrium(III) yields a complex of the macrobicyclic ligand. L6H3, [Y(L6H3)(H2O)2](CIO4)3, the single crystal X-ray structure of which is described. [La(L6H3)(H2O)](CIO4)3 was further reacted with Ni(CIO4)2 in the presence of N,N-diisopropylethylamine to form the heterobimetallic complex [LaNi(L1)(H2O)](CIO4)2, the structure of which was confirmed by single crystal X-ray analysis. Preliminary magnetic studies on the complex [GdNi(L1)](CIO4)2 indicate a weak ferromagnetic coupling between the metals.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available