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This dissertation, "Novel Luminescent Cyclometalated Gold (III) Alkynyls: Design, Synthesis, Photophysics and Their Multinuclear Assemblies" by Ling-ling, Hung,, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled NOVEL LUMINESCENT CYCLOMETALATED GOLD(III) ALKYNYLS - DESIGN, SYNTHESIS, PHOTOPHYSICS AND THEIR MULTINUCLEAR ASSEMBLIES Submitted by HUNG Ling Ling for the Degree of Doctor of Philosophy at The University of Hong Kong in November 2007 A new class of luminescent mononuclear cyclometalated gold(III) complexes containing various monoynyl ligands, [Au(RC DEGREESN(R′) DEGREESCR)(C≡CR′′)], i.e. [Au(C DEGREESN DEGREESC)(C≡CR′′)] (HC DEGREESN DEGREESCH = 2,6-diphenylpyridi≠ R′′ = C H, C H-Cl-p, 6 5 6 4 C H-C H -p, C H-OCH -p, C H-NO -p, C H-NH -p, C H-N(CH ) -p, 6 4 6 13 6 4 3 6 4 2 6 4 2 6 4 3 2 t t t t C H-N(C H ) -p, C H ), [Au( BuC DEGREESN DEGREESC Bu)(C≡CR′′)] (H BuC DEGREESN DEGREESCBuH = 2,6- 6 4 6 5 2 6 13 bis(4-tert-butylphenyl)pyridi≠ R′′ = C H, C H-NH -p, Si(CH ), H), 6 5 6 4 2 3 3 [Au(FC DEGREESN DEGREESCF)(C≡CR′′)] (HFC DEGREESN DEGREESCFH = 2,6-bis(4-fluorophenyl)pyridi≠ R′′ = C H, 6 5 C H-NH -p) and [Au(C DEGREESNTol DEGREESC)(C≡CC H-C H -p)] (HC DEGREESNTol DEGREESCH = 2,6- 6 4 2 6 4 6 13 diphenyl-4-p-tolylpyridine) have been synthesized. Most of the complexes have been structurally determined by X-ray crystallography which revealed the presence of intermolecular Π-Π stacking interaction with interplanar separations between [Au(RC DEGREESN(R′) DEGREESCR)] units of ca. 3.343-3.570 A. The lowest-lying excited states of 3 these complexes in d