Platinum Ii And Palladium Ii Complexes Of Some Phosphine Nitrile Ligands PDF Download

This dissertation, "Luminescent Palladium(II) and Platinum(II) Complexes With Tridentate Monoanionic and Tetradentate Dianionic Cyclometallated Ligands: Structures, Photophysical Properties and Material Application" by Pui-keong, Chow, 周沛強, 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: Four structural isomers of platinum(II) complexes with C-deprotonated R-C DEGREESN DEGREESN-R' cyclometallated ligands (R-C DEGREESN DEGREESN-R' = -extended 6-aryl-2,2'-bipyridine derivatives containing 2-naphthyl, 3-isoquinolinyl, 1-isoquinolinyl or 2-quinolinyl moieties) have been synthesized with their photophysical properties investigated. The one bearing a 3-isoquinolinyl moiety shows the highest emission quantum yield among the four and hence has been extensively modified to give a series of complexes with different ancillary ligands (chloride, iodide, phenoxide, or acetylide). Most of these complexes show vibronic emission (max = 515-644 nm) with high emission quantum yield (up to unity) in degassed CH2Cl2; one of them has been used for OLED fabrication and shows a maximum EQE of 8.15 % with current efficiency of 25 cd A-1. The photocatalytic properties of these derivative complexes for oxidative tertiary amine functionalization have also been examined. Several highly robust and emissive platinum(II) complexes supported by two types of tetradentate O DEGREESN DEGREESC DEGREESN ligand systems (Φem up to 0.99; Td up to 520 ℃) have been synthesized and show different emission energies (λmax = 482-561 nm). Most of them exhibit excimeric emission in solution state at room temperature which are dependent on the modifications on the tetradentate O DEGREESN DEGREESC DEGREESN ligands. DFT/TDDFT calculations reveal that the metal complex showing the most intense excimeric emission possesses an excimeric excited state with a localized structure, which is unusual for these classes of platinum(II) complexes. Based on this finding, WOLED (ηL(max) = 71.0 cd/A, ηp(max) = 55.8 lm/W, ηExt = 16.5 %, CIE = 0.33, 0.42, CRI = 77) and WPLED (ηL(max) = 17.0 cd/A, ηp(max) = 9.1 lm/W, ηExt = 9.7 %, CIE = 0.43, 0.45, CRI = 78) based on this complex have been fabricated with high efficiency achieved. Palladium(II) complexes containing C-deprotonated R-C DEGREESN DEGREESN-R' cyclometallated and pentafluorophenylacetylide ligands exhibit phosphorescence in both solid state and fluid solutions at room temperature with some of them exhibiting aggregation-induced emission (AIE). These complexes have been applied as photosensitizers in light-induced oxidative functionalization of secondary and tertiary benzylic amines as well as in light-induced hydrogen production, with a maximum of 175 turnovers for hydrogen produced. Palladium(II) complexes containing two types of tetradentate dianionic O DEGREESN DEGREESC DEGREESN ligand systems (Systems 1 and 2) have been prepared and show constrasting photophyical properties. A full scale time-resolved spectroscopic analysis has been done on some of these complexes and a platinum(II) analogue. These complexes are found to have similar excited state decay pathway( 〖S_1〗 DEGREESi→〖S_1〗 DEGREESf→T) with ΦISC of about unity. The emission efficiency of System 2 complexes is superior to that of System 1 complexes, which is ascribed to the suppression of excited state distortion on the basis of the results of DFT calculations. A lower radiative decay rate of System 2 palladium(II) complexes relative to the platinum(II) analogue has been found, which could be due to their lower spin-orbit coupling constant. One of the palladium(II) complexes ha