published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

Atomically thin group-VI transition metal dichalcogenides (TMDC) has been emerging as a family of intrinsic 2-dimensional (2D) crystals with a sizeable bandgap in the visible and near infrared range, satisfying numerous requirements for ultimate electronics and optoelectronics. This intrinsic 2D crystal also provides a perfect platform for physics study in 2D semiconductors. The characteristic inversion symmetry breaking presented in monolayer TMDCs leads to non-zero but contrasting Berry curvatures and orbital magnetic moments at K/K’ valleys located at the corners of the first Brillouin zone. These features provide an opportunity to manipulate electrons’ additional internal degrees of freedom, namely the valley degree of freedom, making monolayer TMDC a promising candidate for the conceptual valleytronics. Besides, the strong spin-orbit interactions and the subsequent spin-valley coupling demonstrated in 2D TMDCs open potential new routes towards quantum manipulation. In this thesis, I give a brief review on the background and our progress of the physics study in 2D TMDCs (MoS2, WS2) via optical spectroscopy. Particularly, our experimental approach on the excitonic effect, valley dependent circular dichroism, and the spin-valley coupling in monolayer and bilayer TMDCs are elaborated in individual chapters. / published_or_final_version / Physics / Doctoral / Doctor of Philosophy

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This thesis deals with the applications of organopalladium and organochromium chemistry to the functionalisation of the benzopyran ring system, at a variety of oxidation levels. Section I demonstrates the functionalisation of 3-, 6-, and 8-bromochromones via palladium (0) insertion into the C-Br bond. The resultant arylpalladium species are shown to undergo addition to the least substituted end of a variety of olefins including methyl acrylate, acrylonitrile and styrene. Subsequent palladium-hydride elimination leads to overall palladium catalysed vinylation of the chromone and the synthesis of a number of novel compounds. Vinylation occurs regiospecifically at the site of chromone bromination and is shown to allow clean substituent introduction into each of the three sites. The palladium catalysed reaction of 3,6-dibromo-chromone with methyl acrylate leads to vinylation at both the C3 and C6 positions. Carbonylation of the 6-bromochromone in ethanol or butanol leads to the 6-ethyl or 6-butyl esters respectively. The palladium catalysed vinylation of the 6-bromochromone with ethyl vinyl ether leads to a mixture of products from addition of the chromone to either end of the olefin. With p-bromophenol or p-bromo-N,N-dimethylaniline the reaction gives exclusively the acetylated product arising from addition to the more substituted end of the olefin. This change in orientation is rationalised by considering the polarisation of the olefin and the arylpalladium species. Section II demonstrates the functionalisation of chroman and 4-chromanol via coordination to the Cr(CO)₃ moiety. (η⁶-Chroman)Cr(CO)₃ is synthesised and is shown to undergo regiospecific ring deprotonation at C8 under kinetic conditions or regiospecific benzylic deprotonation at C4 under thermodynamic conditions. The resultant anions are quenched with alkyl halides, aldehydes, Eschenmoser's salt and methyl disulphide resulting in selective functionalisation of either site. No mixed products are observed. The uncomplexed arene is shown to be totally unreactive under identical conditions. (η⁶-4-Chromanol)Cr(CO)₃ is synthesised and is shown to undergo regiospecific C8 ring deprotonation by comparison with authentic samples of the C5 and C8 methylated alcohols. Protection of the hydroxyl group as its methyl, t-butyldimethylsilyl or methoxymethyl ethers is found not to alter the regiochemistry of deprotonation. The 4-chromanol t-butyldimethylsilyl and tri-i-propylsilyl ethers are synthesised and coordinated to the metal unit. Cleavage of the silyl ethers is shown to proceed with loss of stereochemistry, indicating C-0 bond cleavage.

Typescript (photocopy) / viii, 283 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980

Title on spine: Transition metal complexes / 173 leaves : ill., tables, graphs ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.1979) from the Dept. of Physical and Inorganic Chemistry, University of Adelaide

Typescript (photocopy) / 2 microfiche in end pocket / 190 leaves : ill. ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1984

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1980. / Typescript (photocopy).

Thesis (Ph.D.) -- University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1984. / Typescript (photocopy). 2 microfiche in end pocket.