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Title: Functionalization of endohedral fullerenes and their application in quantum information processing
Author: Liu, Guoquan
ISNI:       0000 0004 2728 0583
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2011
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Quantum information processing (QIP), which inherently utilizes quantum mechanical phenomena to perform information processing, may outperform its classical counterpart at certain tasks. As one of the physical implementations of QIP, the electron-spin based architecture has recently attracted great interests. Endohedral fullerenes with unpaired electrons, such as N@C60, are promising candidates to embody the qubits because of their long spin decoherence time. This thesis addresses several fundamental aspects of the strategy of engineering the N@C60 molecules for applications in QIP. Chemical functionalization of N@C60 is investigated and several different derivatives of N@C60 are synthesized. These N@C60 derivatives exhibit different stability when they are exposed to ambient light in a degassed solution. The cyclopropane derivative of N@C60 shows comparable stability to pristine N@C60, whereas the pyrrolidine derivatives demonstrate much lower stability. To elucidate the effect of the functional groups on the stability, an escape mechanism of the encapsulated nitrogen atom is proposed based on DFT calculations. The escape of nitrogen is facilitated by a 6-membered ring formed in the decomposition of the pyrrolidine derivatives of N@C60. In contrast, the 4-membered ring formed in the cyclopropane derivative of N@C60 prohibits such an escape through the addends. Two N@C60-porphyrin dyads are synthesized. The dyad with free base porphyrin exhibits typical zero-field splitting (ZFS) features due to functionalization in the solid-state electron spin resonance (ESR) spectrum. However, the nitrogen ESR signal in the second dyad of N@C60 and copper porphyrin is completely suppressed at a wide range of sample concentrations. The dipolar coupling between the copper spin and the nitrogen spins is calculated to be 27.0 MHz. To prove the presence of the encapsulated nitrogen atom in the second dyad, demetallation of the copper porphyrin moiety is carried out. The recovery of approximately 82% of the signal intensity confirms that the dipolar coupling suppresses the ESR signal of N@C60. To prepare ordered structure of N@C60, the nematic matrix MBBA is employed to align the pyrrolidine derivatives of N@C60. Orientations of these derivatives are investigated through simulation of their ESR spectra. The derivatives with a –CH3 or phenyl group derived straightforward from the N-substituent of the pyrrolidine ring are preferentially oriented based on their powder-like ESR spectra in the MBBA matrix. An angle of about is also found between the directors of fullerene derivatives and MBBA. In contrast, the derivatives with a –CH₂ group inserted between the phenyl group and the pyrrolidine ring are nearly randomly distributed in MBBA. These results illustrate the applicability of liquid crystal as a matrix to align N@C60 derivatives for QIP applications.
Supervisor: Briggs, G. Andrew D. ; Porfyrakis, Kyriakos ; Khlobystov, Andrei N. ; Ardavan, Arzhang Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Nanomaterials ; Physical & theoretical chemistry ; Quantum information processing ; Endohedral fullerene ; electron spin resonance ; quantum information processing ; radical pair ; electron-elctron coupling ; porphyrin