This dissertation, "Design and Synthesis of Luminescent Metal Polypyridyl Complexes of Platinum(II), Ruthenium(II) and Osmium(II) for Chemosensing and Biological Studies" by Wing-suen, Tang, 鄧詠璇, 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 METAL POLYPYRIDYL COMPLEXES OF PLATINUM(II), RUTHENIUM(II) AND OSMIUM(II) FOR CHEMOSENSING AND BIOLOGICAL STUDIES Submitted by TANG WING SUEN for the degree of Doctor of Philosophy at The University of Hong Kong in November 2006 A series of platinum(II) terpyridyl alkynyl complexes derivatized with basic amino functionalities and crown ether pendants, [Pt(trpy)(C≡C-R)]X (R = - - -C H -N(CH ) -4, X = OTf; R = -C H -N(CH CH OCH ) -4, X = OTf; R = 6 4 3 2 6 4 2 2 3 2 - - -C H -NH-4, X = OTf; R = -C H -N(CH )-4, X = Cl; R = 6 4 2 6 4 3 2 - - -C H -N(CH CH OCH ) -4, X = Cl; R = -C H -NH -4, X = Cl; R = -B15C5, X 6 4 2 2 3 2 6 4 2 - - = OTf; R = -A15C5, X = OTf ) have been synthesized. The X-ray crystal structure of [Pt(trpy){C≡CC H -N(CH CH OCH )-4}](OTf) has been 6 4 2 2 3 2 determined. The lowest energy absorption of the complexes except [Pt(trpy)(C≡CB15C5)](OTf) were tentatively assigned to originate from a π(C≡C) → π*(trpy) ligand-to-ligand charge transfer (LLCT) transition mixed with some metal-to-ligand charge transfer (MLCT) contribution. The ion-binding and pH dependent properties have also been studied. Their photophysical and spectroscopic properties were shown to be dependent on pH and selected metal ions, and their colorimetric and luminescence chemosensing properties were described. Another series of platinum(II) terpyridyl alkynyl complexes, t - [Pt( Bu trpy)(C≡C-R)]X [R = -C H -NH -4, X = OTf; R = -C H -NCS-4, X = 3 6 4 2 6 4 - - - OTf; R =-C H -NHCOCH I-4, X = OTf; R = -UH-5 (UH = Uracil), X = Cl; 6 4 2 -UMe-5, X = OTf (UMe = 1,3-dimethyluracil)] have been successfully synthesized and characterized. The X-ray crystal structures of t t [Pt( Bu trpy)(C≡C-C H-NCS-4)](OTf), [Pt( Bu trpy)(C≡C-UH-5)]Cl and 3 6 4 3 [Pt( Bu trpy)(C≡C-UMe-5)](OTf) have been determined. Their photophysical and electrochemical behaviour, together with their protein labeling and DNA binding studies, have also been studied. The emission of the complexes in solution at room temperature has been tentatively assigned as originated from a dπ(Pt) → π*( Bu trpy) triplet MLCT excited state. The 77 K butyronitrile glass displayed dual luminescence which were assigned to originate from an intraligand (IL) phosphorescence of the terpyridine ligand and a dπ(Pt) → t 3 t π*( Bu trpy) MLCT phosphorescence. The [Pt( Bu trpy)(C≡C- 3 3 C H-NHCSNH-4)](OTf)-HSA and [Pt( Bu trpy)(C≡C-C H -NHCOCH S- 6 4 3 6 4 2 4)](OTf)-HSA (HSA = human serum albumin) bioconjugates were highly colored and exhibited luminescence in the visible region upon photoexcitation. A series of ruthenium(II) diimine complexes and an osmium(II) diimine complex containing extended π-conjugated ligands, [Ru(bpy) (pmra)](PF ) 2 6 2 [pmra = N-(2-pyridylmethylene)-2-fluorenamine], [Ru(bpy) (pmra)]Cl, 2 2 [Ru(bpy) (pmaa)]Cl [pmaa = N-(2-pyridylmethylene)-2-anthramine], 2 2 [Ru(bpy) (pmpa)]Cl [pmpa = N-(2-pyridylmethylene)-1-pyrenamine], 2 2 [Ru(bpy) (pmfa)]Cl [pmfa = N-(2-pyridylmethylene)-3-fluoranthenamine] 2 2 and [Os(bpy) (pmaa)](PF ), have been synthesized. The lowest energy 2 6 2 absorption bands of the ruthenium(II) complexes w