Carbon Nanostructures – from Molecules to Functionalised Materials : Fullerene-Ferrocene Oligomers, Graphene Modification and Deposition

The work described in this thesis concerns development, synthesis and characterisation of new molecular compounds and materials based on the carbon allotropes fullerene (C60) and graphene. A stepwise strategy to a symmetric ferrocene-linked dumbbell of fulleropyrrolidines was developed. The versatility of this approach was demonstrated in the synthesis of a non-symmetric fulleropyrrolidine-ferrocene-tryptophan triad. A new tethered bis-aldehyde, capable of regiospecific bis-pyrrolidination of a C60-fullerene in predominantly trans fashion, was designed, synthesised and reacted with glycine and C60 to yield the desired N-unfunctionalised bis(pyrrolidine)fullerene. A catenane dimer composed of two bis(pyrrolidine)fullerenes was obtained as a minor co-product. From the synthesis of the N-methyl analogue, the catenane dimer could be separated from the monomeric main product and fully characterised by NMR spectroscopy. Working towards organometallic fullerene-based molecular wires, the N-unfunctionalised bis(pyrrolidine)fullerene was coupled to an activated carboxyferrocene-fullerene fragment by amide links to yield a ferrocene-linked fullerene trimer, as indicated by mass spectrometry from reactions carried out at small scale A small library of conjugated diarylacetylene linkers, to be coupled to C60 via metal-mediated hydroarylation, was developed. Selected linker precursors were prepared and characterised, and the hydroarylation has been adapted using simple arylboronic acids. Few-layer graphene was prepared and dip-deposited from suspension onto a piezoelectric polymer substrate. Spontaneous side-selective deposition was observed and, from the perspective of non-covalent interaction, rationalised as being driven by the inbuilt polarization of the polymer. Aiming for selectively edge-oxidized graphene, a number of graphitic materials were treated with a combination of ozone and hydrogen peroxide under sonication. This mild, metal-free procedure led to edge-oxidation and exfoliation with very simple isolation of clean materials indicated by microscopy, spectroscopy, and thermogravimetric analysis