This dissertation, "Design and Synthesis of Luminescent Mono- and Dinuclear Platinum(II) Alkynyl Terpyridine Complexes: From Photophysics to Aggregation and Self-assembly" by Hoi-yiu, Chan, 陳凱耀, 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 DESIGN AND SYNTHESIS OF LUMINESCENT MONO- AND DINUCLEAR PLATINUM(II) ALKYNYL TERPYRIDINE COMPLEXES - FROM PHOTOPHYSICS TO AGGREGATION AND SELF-ASSEMBLY submitted by CHAN Hoi Yiu for the degree of Doctor of Philosophy at The University of Hong Kong in August 2006 A series of mononuclear alkynylplatinum(II) terpyridyl complexes, [Pt(trpy)({C{ C} C H )]PF, [Pt(trpy)({C{ C} C H CF -4)]PF, n 6 5 6 n 6 4 3 6 [Pt(trpy)({C{ C} C H CH -4)]PF, and [Pt( Bu trpy)(C{ C C{ C C H )]PF (n = n 6 4 3 6 3 6 5 6 2, 3), have been synthesized. The X-ray crystal structures of the two forms of [Pt(trpy)(C{ C C{ C C H )]PF, [Pt(trpy)(C{ C C{ C C{ C C H CH -4)]PF and 6 5 6 6 4 3 6 [Pt( Bu trpy)(C{ C C{ C C H )]PF have been determined. Dinuclear and 3 6 5 6 trinuclear alkynylplatinum(II) terpyridyl complexes, [1,4- {Pt(trpy)C{ C} C H ](OTf), [1,4-{Pt( Bu trpy)C{ C} C H ](OTf), [2,5- 2 6 4 2 3 2 6 4 2 {Pt(trpy)C{ C} C H S](OTf), [2,5-{Pt( Bu trpy)C{ C} C H S](OTf) and [1,3,5- 2 4 2 2 3 2 4 2 2 {Pt( Bu trpy)C{ C} C H ](OTf) have been successfully synthesized. The X-ray 3 3 6 3 3t crystal structure of [1,4-{Pt( Bu trpy)C{ C} C H ](OTf) has also been 3 2 6 4 2 determined. The luminescence properties of these complexes have been studied and their lowest-lying excited states in fluid solution and in the glass state were tentatively assigned as admixture of MLCT [dS (Pt)ĺ S *(trpy)] and LLCT [S (C{ C)ĺ S *(trpy)] origin, whereas the low-energy emissions in the solid state were attributed to triplet metal metal-to-ligand charge transfer ( MMLCT) phosphorescence, resulting from significant Pt---Pt interactions in the solid state. Besides, a series of luminescent platinum(II) terpyridyl alkynyl complexes with different counter anions, [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF, ClO, 6 4 BF, BPh ), [Pt(trpy)(C{ C C H )]X (X = OTf, PF, ClO, BF ) and 4 4 6 5 6 4 4 complexes with various substituents on the alkynyl and terpyridyl ligands, [Pt(trpy)(C{ CC H OCH-4)]OTf, [Pt(4'-CH O trpy)(C{ C C H )]OTf, 6 4 3 3 6 5 [Pt( Bu trpy)(C{ C C{ CH)]OTf, [Pt(trpy)(C{ CC H {CH NMe }-4)](OTf), 3 6 4 2 3 2 [Pt(trpy)(C{ C C{ C CH NMe )](OTf) and [Pt(trpy)(C{ C C{ C CH OH)]OTf 2 3 2 2 have been synthesized and their photophysical properties have been stuided. The X-ray crystal structure of [Pt(trpy)(C{ C C H )]ClO and 6 5 4 [Pt( Bu trpy)(C{ C C{ C H)]OTf have been determined. The solid-state absorption and emission spectra showed low-energy bands, which were assigned as derived from MMLCT origin. Solvent-induced aggregation studies of these complexes in solution showed that the color of the aggregates could be very different for different counter-ions, indicating that counter-ions played an important role in governing the degree of aggregation and the extent of interactions within these aggregates. Addition of various anions to solutions of [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF ) produced anion-induced color 6changes upon solvent-induced aggregation, showing that these complexes might serve as potential colorimetric anion probes. The effect of temperature on the aggregation properties of the complexes has also been explored. New low-energy absorption and emission bands were found upon a reduction of temperature, attributable to the formation o