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Title: Investigations into hybrids of carbon nanotubes and organo-metallic molecular systems
Author: Lewis, Peter
Awarding Body: University of Bath
Current Institution: University of Bath
Date of Award: 2013
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Endohedral functionalization via supercritical CO2 was undertaken in order to produce encapsulation of organometallic systems that are difficult to encapsulate otherwise due to either their large size or extreme air sensitivity. Organometallic molecular systems from the prophyrin and phthalocyanine families (such as NiPc, ClAlPc and NiTPP) were successfully encapsulated inside of nanotubes with relatively large diameters (centred around 2 nm). This was assessed by a combination of high resolution transmission electron microscopy (HRTEM) and Raman spectroscopy. HRTEM revealed previously unreported ordering of NiTPP, a large planar molecule, in row-like assemblies inside nanotubes of diameters that match best the geometrical size of the molecule (2 nm), highlighting the role of confinement in promoting assembly. Using both endohedral and exohedral functionalization with NiTPP, ClAlPc and NiPc molecules provided a set of systems differing by only one specific parameter (e.g. central ion or body type, or size of the HOMO-LUMO gap), or comparatively affected the ability to bind to the nanotubes - the associated changes in the electronic properties of the nanotubes were revealed by resonant Raman spectroscopy. These changes were interpreted in terms of ability of the guest molecular species to produce charge transfer to/from the nanotube, and/or induce structural strain.
Supervisor: Not available Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available