This dissertation, "Iridium Porphyrin Complexes Containing Alkynyl, Carbene and Allenylidene Ligands" by Tsz-lung, Lam, 林子龍, 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 IRIDIUM PORPHYRIN COMPLEXES CONTAINING ALKYNYL, CARBENE AND ALLENYLIDENE LIGANDS Submitted by Lam Tsz Lung for the degree of Doctor of Philosophy at The University of Hong Kong in November 2013 Transition metal complexes containing π-conjugated carbon-rich ligands constitute an important class of organometallic complexes. This thesis focuses on the synthesis, bonding, spectroscopic studies and other properties of iridium porphyrin complexes bearing σ-alkynyl, NHC, Fischer type carbene and allenylidene ligands. A series of σ-alkynyl complexes of iridium porphyrin Ir(por)C≡CAr (por = ttp, oep, tmp, F tpp; Ar = Ph, 4-PhC H, 4-OMeC H, 4-FC H, 4-CF C H, 20 6 4 6 4 6 4 3 6 4 4-NMe C H, 2-naphthyl, 1-pyrenyl, 9,9-dibutyl-9H-fluoren-2-yl) were prepared 2 6 4 by reacting Ir(por)Cl(CO) with lithium arylacetylide or a mixture of HC≡CPh, CuI and Et N in good yields. The hexa-coordinated mononuclear alkynyl complexes Ir(por)C≡CAr(L) (L = m-XylylNC, py, PPh, I Pr) and binuclear 3 alkynyl complex [Ir(oep)C≡CPh] L' (L' = 1,4-diisocyanobenzene) were obtained upon the addition of ligand L or L'. Five of these complexes including the dinuclear congener were structurally characterized by X-ray crystallography. Variations of the ν(C≡C) and Ir-C bond lengths among the alkynyl alkynyl complexes are suggested to be the result of different extent of Ir → C π back alkynyl donation, which is dependent on the electronic properties of ligand L. The alkynyl complexes are emissive in the range of red to NIR in the fluid and glass states. In particular, in the oep analogue, the incorporation of isocyanide ligand led to a significant enhancement of the luminescence quantum efficiency (Ф up to em 0.085). Preliminary studies suggested that Ir(ttp)C≡CPh is a good catalyst for carbenoid transfer/insertion reactions. Reactions of Ir(por)Cl(CO) with bis(NHC)silver complexes gave rise to a series of novel mono(NHC)iridium porphyrin complexes Ir(por)(NHC)Cl (por = tmp, F tpp; NHC = IMe, BIMe) or [Ir(por)(NHC)(OH )] (por = ttp, tmp; NHC = 20 2 i + I Pr, IMe, BIMe) and bis(NHC) complexes [Ir(por)(NHC) ] (por = ttp, oep, F tpp; NHC = IMe, BIMe) in good to excellent yields. Preliminary study 20 suggested that the NHC ligands of (NHC)iridium porphyrin complexes were inert towards ligand substitution. Spectroscopic and electrochemical studies supported the fact that the NHC ligand is a strong σ donor. (NHC)iridium porphyrin complexes showed unusual double Soret bands. The extra Soret band originated 1 + from a MLCT state according to TDDFT calculations. [Ir(oep)(BIMe) ] and i + [Ir(oep)(I Pr) ] exhibited pronounced ruffling distortion of the porphyrin rings as revealed by their X-ray crystal structures. Significantly, [Ir(oep)(BIMe) ] showed extensive intermolecular π stacking between the NHC ligands, leading to the formation of one dimensional polymeric chain. Moreover, its SEM/TEM images displayed self-assembled nano-fibre or nano-plate structures depending on the counteranion and solvent system. (NHC)iridium porphyrin complexes exhibited photophysical properties similar to other non-planar metalloporphyrin complexes, including large Stokes shifts, broad emission bands, short-lived and weakly emissive T states. Iridium porphyrin complexes containing Fischer