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Title: Self-assembly and host-guest studies of heteronuclear coordination complexes
Author: Metherell, A. J.
ISNI:       0000 0004 5356 394X
Awarding Body: University of Sheffield
Current Institution: University of Sheffield
Date of Award: 2014
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This thesis is primarily concerned with the synthesis and characterisation of heterometallic polynuclear coordination structures, but also contains host-guest studies of mononuclear complexes. Chapter One consists of an introduction to self-assembly and supramolecular chemistry. Recent examples of coordination cages are given along with previous work from the Ward group. An introduction to recent efforts in the field of heterometallic supramolecular chemistry is also given. Chapter Two describes the use of a series of mononuclear Ru(II) complexes to act as models for the vertices of coordination cages. A simple and general synthetic procedure is described which will allow access to a wide range of substituted analogues of [Ru(LH)3]2+ as their pure fac and mer isomers. It has been shown that the fac-[RuL3]2+ complexes bind to isoquinoline N-oxide more strongly than the mer isomer, but much less strongly than the complete cage complex due to the presence of competing anions, which are excluded from the cage cavity. Chapter Three describes the formation of a series of heteronuclear coordination cages from inert and labile subcomponents. The synthesis of a range of mononuclear [RuL2]2+ and [RuL3]2+ complexes as either a mixture of mer and fac isomers or pure fac is discussed, followed by the self-assembly of two heterometallic cubes [Ru4Cd4(L1,5-nap)12]16+ and [Ru4Co4(Lm-Ph)12]16+, a [Ru4Cd12(Lp-Ph)12(L1,4-nap)12]32+ cage, the adamantoid cage [{Ru(Lp-Ph)3}4Ag6]14+, and the trinuclear [{Ru(Lo-Ph)2}2Ag]5+. Chapter Four describes the syntheses and characterisation of a family of asymmetric ligands based upon pyrazolyl-pyridine and catecholamide binding moeties connected by aromatic spacers. The synthesis and structural determination of a tetrameric hetero-octanuclear cyclic helicate [Ti4Zn4(L1,3)8(μ-OMe)8] with the ligand H2L1,3 is described. Chapter Five describes the efforts towards functionalising the exterior of M8L12 cages. The synthesis of the aniline functionalised ligand Lan is discussed, which self-assembles with Co(II) to form a [Co8(Lan)12]16+ cube. Functionalising the ligand with ferrocene to form LFc results in the self-assembly process with Co(II) now forming a [Co6(LFc)9]12+ structure.
Supervisor: Ward, M. D. Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available