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| Author | : Claudio Pio Mastrocinque |
| Publisher | : |
| Total Pages | : 0 |
| Release | : 2019 |
| Genre | : Chemistry, Inorganic |
| ISBN | : |
| Author | : Francesco Mastrocinque |
| Publisher | : |
| Total Pages | : 0 |
| Release | : 2018 |
| Genre | : Carbenes |
| ISBN | : |
Thiophene and benzothiophene ligands containing N-heterocyclic carbene (NHC) moieties were used to synthesize five and six-membered Pt(II) metallacycles. Ligand scaffolding was synthesized using two methods. The five-membered metallacycles were produced using a coupling reaction, utilizing Cu2O as the inorganic catalyst. The six-membered metallacycles were synthesized using a nucleophilic substitution reaction. The ligands were then metalated using chelate-assisted C-H activation. The synthesis, characterization, and photophysical properties of these NHC-functionalized, cyclometalated products are reported.
| Author | : Deepak Ravindranathan |
| Publisher | : |
| Total Pages | : 88 |
| Release | : 2012 |
| Genre | : Chemical bonds |
| ISBN | : |
The synthesis, structure, and photophysical properties of a series of novel, highly luminescent tridentate platinum complexes with general coordination geometry of (C^N*N)-PtL are reported, where "C^N" denotes a coordination of C and N to the platinum to form a five-membered metallacycle and "N*N" denotes a coordination of two N atoms to the platinum to form a six-membered metallacycle; L is a mono anionic ligand such as halides or acetylides. Compared to the known (C^N^N)-PtL type of complexes that were reported to emit with low quantum yields, the structural modification leads to dramatic improvements in phosphorescence efficiency. For example, new complexes (C^N*N)-PtL with L = hexylacetylide and phenylacetylide emitted intensely with quantum yields of 47% and 56%, respectively, latter of which is among the highest quantum yields reported so far for cyclometalated platinum (II) complexes. Selectivity in C-H bond activation by platinum and the exact mechanism of cycloplatination are issues that still remain unclear. A series of ligands which include sp2/sp3, primary/secondary sp3 C-H bonds, and aromatic/vinylic sp2 C-H bonds with a carbon linker between the bipyridine and the carbon groups have been prepared. All ligands have been attempted for cycloplatination in glacial acetic acid and acetonitrile. All ligands produced the same sp2 C-H bond activated complex in both solvents, which suggests that the linker atom does play a role on selectivity.
| Author | : Wai-Yip Tong |
| Publisher | : Open Dissertation Press |
| Total Pages | : |
| Release | : 2017-01-26 |
| Genre | : |
| ISBN | : 9781361342602 |
This dissertation, "Luminescent Platinum(II) Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen, Nitrogen and Carbon Donor Atoms and Platinum(II)-containing Phosphorescent Polymers: Synthesis, Photophysical Properties and Material Applications" by Wai-yip, Tong, 唐煒燁, 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 LUMINESCENT PLATINUM(II) COMPLEXES CONTAINING DIANIONIC TETRADENTATE LIGANDS HAVING MIXED OXYGEN, NITROGEN AND CARBON DONOR ATOMS AND PLATINUM(II)-CONTAINING PHOSPHORESCENT POLYMERS: SYNTHESIS, PHOTOPHYSICAL PROPERTIES AND MATERIAL APPLICATIONS Submitted by TONG WAI YIP for the degree of Doctor of Philosophy at The University of Hong Kong in May 2014 Square planar platinum(II) complexes exhibit rich photophysical properties which are tunable through the structural variation of ligands and can be harnessed for applications in materials science. In this thesis, the great variety of spectroscopic properties of various square planar cyclometalated platinum(II) complexes supported by tetradentate (O DEGREESN DEGREESN DEGREESC and O DEGREESN DEGREESC DEGREESN) and tridentate (C DEGREESN DEGREESN) ligands containing dipyridyl moieties will be highlighted, along with their synthesis, characterization and potential application in organic light emitting diodes (OLEDs). Ind Platinum(II) complexes supported by tetradentate O DEGREESN DEGREESN DEGREESC or O DEGREESN DEGREESN DEGREESC types of ligands (O DEGREESN DEGREESN DEGREESC = 2-(4-(3,5-di-tert-butylphenyl)-6'-phenyl-2,2'- Ind bipyridin-6-yl)phenolate; O DEGREESN DEGREESN DEGREESC = 5,5-dialkyl-2-(6-phenylpyridin-2-yl) indeno[1,2-b]pyridin-9-olate) are emissive in solution at room temperature, with emission maxima tunable from 582 nm to 640 nm and quantum yields up to 0.28. Mechanochromism and the associated luminescence change in [Pt(dihexyl- Ind O DEGREESN DEGREESN DEGREESC)] (Complex 3.6) were found associated with the two different crystal packings revealed by powder X-ray diffraction (PXRD) studies. Fast vapochromic response of [Pt(3-O DEGREESN DEGREESN-2,6-difluoropyridine)] (Complex 3.3) on chloroform or dichloromethane vapours was found to be associated with structural changes in the solid state through PXRD studies. Robust and strongly emissive platinum(II) complexes supported by tetradentate O DEGREESN DEGREESC DEGREESN ligands featuring fused six-five-six membered metallacyclic ring (O DEGREESN DEGREESC DEGREESN = 2-(4-(3,5-di-tert-butylphenyl)-6-(9-(pyridin-2-yl) carbazol-2-yl)pyridin-2-yl)phenol) have been prepared. These platinum(II) complexes are among the most efficient yellow phosphors, with emission maxima ranging from 526 nm to 553 nm and luminescence quantum yields as high as -1 0.47-0.86. A yellow OLED with power efficiency (η ) up to 52 lm W is power demonstrated. In combination with the typical blue emitting iridium(III) 2' bis(4,6-difluorophenyl-pyridinato-N, C ) picolinate (FIrpic), white organic -1 light-emitting diodes (WOLEDs) displayed η up to 61 lm W and reduced power -2 efficiency roll-off at 1000 cd m . Random copolymers with photo-inert backbone poly[(N-vinylcarbazole)-co- ((R-C DEGREESN DEGREESN)Pt)] and poly[(2-(4-tert-butylphenyl)-5-(4-vinylphenyl)-1,3,4- oxadiazole)-co-((R-C DEGREESN DEGREESN)Pt)] (R-C DEGREESN DEGREESN = 3-(6-phenyl-4-(4-vinylphenyl) pyridine-2-yl)-isoquinoline or 3-(4-(4-(dec-9-enyloxy)phenyl)-6-phenylpyridin- 2-yl)isoquinoline) have been synthesized and characterized. Energy transfer between the charge transporting units and emissive (R-C DEGREESN DEGREESN)Pt units was revealed through ICP-MS inve
| Author | : Subhangi Roy |
| Publisher | : |
| Total Pages | : 189 |
| Release | : 2018 |
| Genre | : |
| ISBN | : |
| Author | : 朱明新 |
| Publisher | : Open Dissertation Press |
| Total Pages | : |
| Release | : 2017-01-27 |
| Genre | : |
| ISBN | : 9781374682665 |
This dissertation, "Syntheses, Characterization and Photophysical Properties of Platinum(II) and Gold(I) Complexes Containing Ortho- and Meta-oligo(phenyleneethynylene) Ligands" by 朱明新, Mingxin, Zhu, 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 SYNTHESES, CHARACTERIZATION AND PHOTOPHYSICAL PROPERTIES OF PLATINUM(II) AND GOLD(I) COMPLEXES CONTAINING ORTHO- AND META- OLIGO(PHENYLENEETHYNYLENE) LIGANDS Submitted by Zhu Mingxin for the degree of Doctor of Philosophy at The University of Hong Kong in March 2008 Metal complexes containing oligo(phenyleneethynylene) (PE) are of great importance in photophysics and material science. The syntheses, characterizations and photophysical properties of the light-emitting platinum(II) and gold(I) complexes with flexible ortho- and meta-PE and 2,5-diphenyl-1,3,4-oxadiazole ligands were described. Several novel dinuclear terpyridyl platinum(II) complexes with ortho-PE ligands were synthesized and their crystal structures were determined. The t t 2+ t platinum(II) complexes [( Bu tpy)Pt-(ortho-PE)-Pt( Bu tpy)] ( Bu tpy = 4,4′,4″-tri- 3 3 3 tert-butyl-2,2′ 6′,2″-terpyridine) adopted a helical conformation in their crystal structures, and their phosphorescence recorded in acetonitrile/water mixtures shifted to lower energy with enhanced intensity when the water content increased. A hydrophobic folding process was suggested for the complexes with long ortho-PE(n) (n >= 3), and the red-shifted and enhanced phosphorescence was attributed to inter- and intra-molecular π-π interactions. The mononuclear terpyridine and C DEGREESN DEGREESN capped t + platinum(II) complexes [( Bu tpy)Pt-(ortho-PE)] and [(C DEGREESN DEGREESN)Pt-(ortho-PE)] (HC DEGREESN DEGREESN = 6-phenyl-2,2′-bipyridine) were studied for comparison. A series of mononuclear and dinuclear ortho- and meta-PE gold(I) complexes, [(PCy )Au-(ortho-PE)] (PCy = tricyclohexylphosphine), [(PCy )Au-(ortho-PE)- 3 3 3 Au(PCy)], [(PCy )Au-(meta-PE)] and [(PCy )Au-(meta-PE)-Au(PCy)] were 3 3 3 3 synthesized to examine the effect of ortho- and meta-conjugation. A ππ* emission of the PE ligands was switched on at room temperature by the attachment of [Au(PCy )] fragment due to the heavy atom effect. The delayed fluorescence from the ππ* excited states of the PE ligands was observed, and a triplet-triplet annihilation pathway was proposed. The difference in conjugation of para-, ortho- and meta-PE ligation was examined by comparison of the singlet and triplet emission energies of the gold(I) complexes. By extrapolating the plot of the emission energy against the PE chain length in the complex, the triplet emission energies of poly(ortho-PE) and poly(meta-PE) were estimated to be 530 and 470 nm respectively. These complexes together with the reported [Au(PCy )] complexes containing para-PE ligands, constitute a complete class of [Au(PCy )] supported phenyleneethynylene complexes. 2+ New ortho-PE ligands were used as flexible linkers for [Pt(PEt ) ] moieties 3 2 (PEt = triethylphosphine). Three neutral platinum(II) macrocycles with the maximum ring size of 60 atoms were synthesized and their crystal structures were determined, 31 revealing decreased nuclearity when the ortho-PE length increases. The P NMR spectra of [Pt(PEt ) {ortho-PE(5)}] with a rigid conformation at various temperatures 3 2 are consistent with the calculated spectrum of ABX spin system. A series of platinum(II)-bis(triethylphosphine) complexes containing 2,5- diphenyl-1,3,4-oxadiazole moiety were synthesized, and
| Author | : Dileep Atchyuth Kumar Vezzu |
| Publisher | : |
| Total Pages | : 291 |
| Release | : 2013 |
| Genre | : Platinum compounds |
| ISBN | : |
The synthesis, structure, and photophysical properties of luminescent platinum (II) complexes with different coordination patterns, (C^C*N^N), (N^C*N), (N^N*C) and (N^N^C) are reported, where "C^N or N^N" denotes a bidentate coordination to the platinum to form a five-membered metallacycle and "C*N" denotes a bidentate coordination to the platinum to form a six-membered metallacycle. Sixteen cyclometalated platinum complexes have been synthesized with different coordination patterns, which include six complexes with tridentate N^C*N cyclometalating ligands (13, 14, 15, 16, 17, and 18), five complexes with N^N*C cyclometalating ligands (19a, 19b, 20a, 20b, and 24), three complexes with N^N^C cyclometalating ligands (21a, 21b, and 29) and two complexes with tetradentate C^C*N^N cyclometalating ligands (33 and 34). The structures of the platinum complexes 13, 15, 16, 18, 19a, 19b, 20a, 21a, 21b, 24, 29, 33, and 39 were determined by single crystal X-ray diffraction. In platinum complexes with five-six membered metallacycle (15, 16, 18, 19a, 19b, 20a, 24, and 39), the square geometry of the complexes is improved when compared to that of platinum complexes with five-five membered metallacycle as the biting angle is increased. The tetradentate coordination (C^C*N^N), square planar geometry of complex 33 are revealed from its X-ray crystal structure. The DFT calculations have been carried out on complexes 13, 14, 15, 16, 17, 18, 33, and 34 to examine the molecular orbital character of the complexes, which are used in interpreting the electronic spectra of the complexes. The photophysical properties of the platinum complexes were studied and a majority of the complexes were highly emissive in solution at room temperature. Complex 13 exhibited the highest quantum yield (65%) among all of the complexes. Self quenching was not observed in a majority of the platinum complexes at lower concentrations. The cytotoxicity (IC50) of the complexes in three lung cancerous cell lines and one prostate cancer cell line were determined by MTT assay. The toxic platinum complexes induced the cell death by triggering apoptosis. The interactions of the platinum complexes with plasmid and calf thymus DNA were studied. Activation of caspase -7, PARP, and p53 were also observed in RV1 and HCC827 cell lines when treated with platinum complexes. Complexes 35, 37 and 38 were more potent than the clinically approved drug, cis-platin.
| Author | : Chi-Kin Koo |
| Publisher | : |
| Total Pages | : 498 |
| Release | : 2008 |
| Genre | : Complex compounds |
| ISBN | : |
| Author | : |
| Publisher | : |
| Total Pages | : 524 |
| Release | : 2011 |
| Genre | : Complex compounds |
| ISBN | : |
| Author | : Michael Weinstein |
| Publisher | : |
| Total Pages | : 0 |
| Release | : 2013 |
| Genre | : Catalysis |
| ISBN | : |
