Download or read book Self assembly of Platinum II Complexes with Tunable Photophysical Properties in Confined Spaces and in Solution written by Rémi Rouquette and published by . This book was released on 2017 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis focuses on the design, synthesis and the photophysical characterisation of luminescent neutral platinum(II) compounds containing a tridentate chromophoric ligand and a monodentate ancillary moiety with different functionalities. Such complexes exhibited drastic changes to their photoluminescence properties upon self-assembly, triggered by the establishment of weak noncovalent p-p stacking and metallophilic interactions. It was demonstrated that these platinum(II) complexes can be covalently attached to silicon and gold substrates but also encapsulated into polymer particles. The self-assembly properties of amphiphilic platinum(II) complexes have also been intensively studied. Understanding the behaviour of one complex in a solvent mixture allowed further investigation into the supramolecular co-assembly of two different platinum(II) complexes. This approach leads to the formation of solvatochromic fibers with specific and reversible phototophysical properties. The investigated compounds and their assemblies were useful for the development of novel functional materials for sensing or stimuli-responsiveness applications.

Download or read book Luminescent Platinum ii Palladium ii and Gold iii Complexes Containing Isocyanide Alkynyl and N Heterocyclic Carbene Ligands written by Faan-Fung Hung and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Luminescent Platinum(II), Palladium(II) and Gold(III) Complexes Containing Isocyanide, Alkynyl and N-heterocyclic Carbene Ligands: Synthesis, Photophysical Properties and Material Applications" by Faan-fung, Hung, 孔繁峰, 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: Several cyclometalated Pt(II) isocyanide complexes containing C-deprotonated C DEGREESN DEGREESC ligands (C DEGREESN DEGREESC = 2,6-diphenylpyridine derivatives) were synthesized. These complexes display orange-red emissions with max at 582-619 nm and quantum yields of up to 26% in CH2Cl2 at room temperature. The incorporation of carbazole/fluorene/thiophene unit(s) to C DEGREESN DEGREESC ligands leads to minimized structural distortion of complexes in their excited states and thereby suppresses non-radiative decay pathways. The high thermal stability (Td >300 C) renders these complexes good candidates as phosphorescent dopants in organic light-emitting diodes (OLEDs). Red-emitting OLEDs with CIE coordinates of (0.650.01, 0.350.01) were fabricated by vacuum deposition, showing a maximum external efficiency of 12%. In addition, well-defined nano/microstructures were obtained from self-assembly of these complexes driven by π∙∙∙π, C-H∙∙∙π and C-H∙∙∙H-C interactions as observed in the crystal structures. Two series of organopalladium(II) alkynyl complexes containing a terpy (terpy = 2,2':6',2''-terpyridine) or C DEGREESN DEGREESC pincer carbene ligand (C DEGREESN DEGREESC = 2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) were prepared. These complexes are non-emissive in solution at room temperature except that the one containing both C DEGREESN DEGREESC and pyrenylacetylide ligands shows phosphorescence (Φ = 0.3%) originating from intraligand state of the acetylide ligand. This could be attributed to the strong -donating N-heterocyclic carbene (NHC) in the pincer ligand that strongly destabilizes d-d state, the population of which provides an efficient non-radiative decay channel. To make comparison between Pd(II) and Pt(II) complexes with the two ligand systems, Pt(II) C DEGREESN DEGREESC alkynyl complexes were also prepared. They are emissive in solution and some display excimer emissions at high concentration (〖10〗 DEGREES(-4)-〖10〗 DEGREES(-3) mol 〖10dm〗 DEGREES(-3)). The X-ray crystal structures of [Pd(L)(CCPh)](〖PF〗_6) (L = terpy and C DEGREESN DEGREESC) revealed one-dimensional chain stacking of complex cations with alternating Pd(II)∙∙∙Pd(II) contacts of about 3.29-3.35 A and π-π interactions of about 3.4 A . Well-defined submicron/nanostructures were obtained from self-assembly of Pd(II) and Pt(II) alkynyl complexes driven by π-π interactions between aromatic moieties and/or metal∙∙∙metal interactions. DFT calculations on the optimized structures of [M(L)(CCPh)]+ (M = Pd(II) and Pt(II)) revealed the existence of metal∙∙∙metal closed-shell interactions. In addition, the complex containing the C DEGREESN DEGREESC ligand exhibits slightly enhanced metal∙∙∙metal interactions and larger "bonding" energy upon dimerization. Furthermore, spin-orbit coupling between singlet and triplet excited states is more effective which promotes rapid intersystem crossing. A new class of cyclometalated Au(III) complexes containing C-deprotonated C DEGREESN ligands (C DEGREESN = 2-phenylpyridine and its derivatives) and cis-chelating bis-NHC ligands was synthesized. These are the first examples of Au(III) complexes supported by cis-chelating bis-NHC ligands. They display emissions in solution under degassed condition at room temperature with &

Download or read book Luminescent Platinum ii Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen Nitrogen and Carbon Donor Atoms and Platinum ii Containing Phosphorescent Polymers written by Wai-Yip Tong and published by Open Dissertation Press. This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Download or read book Design Synthesis Photophysics and Self Assembly Study of Platinum II Terpyridine Complexes and Their Utilization as Stimuli Responsive Smart Materials and Probes for Molecules and Macromolecules of Biological Interest written by Yik-Sham Clive Chung and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis, Photophysics and Self-assembly Study of Platinum (II) Terpyridine Complexes and Their Utilization as Stimuli-responsive Smart Materials and Probes for Molecules and Macromolecules of Biological Interest" by Yik-sham, Clive, Chung, 鍾亦琛, 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: A series of water-soluble platinum(II) terpyridine complexes with functionalized alkynyl ligands and a boronic acid-containing polymer, PAAPBA, have been synthesized and characterized. The photophysical and electrochemical properties of all the platinum(II) complexes have been studied. Some of the complexes have been demonstrated to show ground-state aggregation in organic solvents and aqueous solutions at high concentrations, leading to Pt...Pt and/or π-π interactions and hence the emergence of metal-metal-to-ligand charge transfer (MMLCT) transitions in both the UV-visible and emission spectra. The induced self-assembly of [Pt(tpy)(C≡CC6H4-CH2NMe3-4)](OTf)2 by PAAPBA has been explored for the development of glucose sensing protocols and α-glucosidase assay by monitoring the triplet metal-metal-to-ligand charge transfer (3MMLCT) emission in the near-infrared (NIR) region. [Pt(tpy){C≡CC6H4- {NHC(=NH2])(NH2)}-4}](OTf)2 has been observed to undergo induced aggregation in the presence of citrate, with good selectivity over other mono- and dicarboxylates in the tricarboxylic acid (TCA) cycle. Enzymatic activity of citrate lyase has also been probed by the emission spectral changes of the complex in the NIR region. A series of water-soluble alkynylplatinum(II) terpyridine complexes and water-soluble conjugated polyelectrolytes (CPEs) have been synthesized and characterized. The UV-vis absorption and emission properties of the platinum(II) complexes and CPEs have been investigated in organic solvents and/or aqueous buffer solutions. The electrochemical properties and ground-state aggregation at high concentrations of the platinum(II) complexes have also been examined. Two-component ensembles containing selected platinum(II) complexes and PPE-SO3- have been studied, and Forster resonance energy transfer (FRET) has been demonstrated from the PPE-SO3- donor to the aggregated complexes as acceptors. The ensemble containing PPE-SO3- and [Pt(tpy)(C≡CC6H4CH2NMe3-4)](OTf)2 has been employed for a "proof-of-principle" label-free detection of human serum albumin (HSA) in pH 3 buffer solutions with high selectivity and sensitivity, while another ensemble containing PPE-SO3- and [Pt{tpy(C6H4CH2NMe3-4)-4'}(C≡CC6H5)](OTf)2 has been utilized for selective label-free detection of G-quadruplex structure of the human telomeric DNA in physiological buffer solutions. A series of water-soluble platinum(II) terpyridine complexes with stimuli-responsive alkynyl ligands and a series of water-soluble platinum(II) metallosupramolecular triblock copolymers have been synthesized and characterized. The photophysical and electrochemical properties as well as the ground-state aggregation of the complexes have been investigated. Some of them have been found to show different electronic absorption and emission properties in aqueous solution at different pHs due to aggregation/deaggregation of the complexes. One of the complexes has been employed for live-cell imaging experiments to locate acidic organelles, such as lysosomes, in MDCK cells. The water-soluble platinum(II) metallosupramolecular triblock copolymers have been found to show an increase in 3MMLCT emission intensity in the red-NIR region with temperature, which has been attribu

Download or read book Design and Synthesis of Luminescent Mono And Dinuclear Platinum ii Alkynyl Terpyridine Complexes written by Hoi-Yiu Chan and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Download or read book Synthesis Structure Photophysics and Biological Activity of Platinum II Complexes written by Dileep Atchyuth Kumar Vezzu and published by . This book was released on 2013 with total page 291 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book LUMINESCENT PALLADIUM II PL written by Pui-Keong Chow and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 502 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Download or read book Synthesis Characterization and Photophysical Properties of Cyclometalated Platinum II Complexes written by Claudio Pio Mastrocinque and published by . This book was released on 2019 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Syntheses Characterization and Photophysical Properties of Platinum ii and Gold i Complexes Containing Ortho And Meta Oligo phenyleneethynylene Ligands written by 朱明新 and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Download or read book Design Synthesis and Photophysical Properties of Dinuclear Platinum II Complexes with Varying Bridging and Cyclometalating Ligands written by Subhangi Roy and published by . This book was released on 2018 with total page 189 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Design and Synthesis of Platinum II Complexes with Multidentate N donor Ligands written by 傅莉其 and published by . This book was released on 2017 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book DESIGN SYNTHESIS SPECTROSCOP written by Charlotte Po and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 392 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis and Spectroscopic Studies of Amphiphilic Platinum(II) Complexes With Tridentate N-donor Ligands: From Simple Molecules to Supramolecular Assemblies and Nanostructures" by Charlotte, Po, 布珮樂, 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, SYNTHESIS AND SPECTROSCOPIC STUDIES OF AMPHIPHILIC PLATINUM(II) COMPLEXES WITH TRIDENTATE N-DONOR LIGANDS - FROM SIMPLE MOLECULES TO SUPRAMOLECULAR ASSEMBLIES AND NANOSTRUCTURES Submitted by PO Charlotte for the degree of Doctor of Philosophy at The University of Hong Kong in February 2014 Several series of amphiphilic platinum(II) complexes with tridentate N-donor ligands were synthesized and characterized. Their photophysical properties as well as the spectroscopic changes resulting from the supramolecular assemblies of the complexes were studied. Water-soluble platinum(II) bzimpy complexes have been shown to exhibit strong aggregation in water to give highly ordered nanostructures and by structural modification, various morphologies such as spherical and cylindrical micelles, vesicles and bilayer sheets were obtained. The differences in molecular packing and morphology have been found to give rise to an alteration of Pt---Pt interaction and hence a change in MMLCT absorption and MMLCT emission and such changes were utilized as a probe for the morphological transformation. - + Different hydrophilic groups of sulfonate (-SO ), trimethylammonium (-NMe ) and 3 3 triethylene glycol (TEG) were incorporated into the platinum(II) bzimpy complexes to render their water solubility. An interesting aggregation-partial deaggregation-aggregation process has been demonstrated by [Pt{bzimpy(PrSO ) }Cl]K and its alkynyl analogues via a change in the solvent 3 2 composition. A drastic rainbow-like color change from red to yellow to green and blue was observed via the increase in organic solvent content in the aqueous solution of [Pt{bzimpy(PrSO )}Cl]K. The color change and luminescence change were 3 2 monitored by UV-vis absorption and emission studies, and a change in the MMLCT absorption and emission due to the alteration in Pt---Pt interactions during the assembly and disassembly process was observed. Through microscopy studies, the spectroscopic changes were correlated to a morphological transformation from vesicle to rod. The degree of aggregation of the complexes with different hydrophilic groups was compared through their dimerization constant and the inferences of electrostatic interactions on assemblies were investigated through the modulation of salt content of the solution and via co-assembly studies of the highly charged complexes, [Pt{bzimpy(PrSO ) (OPrSO )}Cl]K and [Pt{bzimpy(C H -NMe ) }Cl]Cl . 3 2 3 2 10 20 3 2 3 Through the incorporation of hydrophilic alkynyl ligands, bolaamphiphilic complexes were also synthesized and their aggregation behavior in water was studied. The effect in tuning the hydrophobicity of the complexes was studied by varying the alkyl chain length of the sulfonate-pendant platinum(II) bzimpy (Pt{bzimpy(PrSO ) }) 3 2 complexes and an unexpected shift in the UV-vis absorption and emission was observed due to the formation of aggregates. The thermo-responsive behavior of a TEG-pendant alkynylplatinum(II) bzimpy complex, [Pt{bzimpy(TEG) }{C≡CC H - 2 6 3 (OC H )-3,5}]Cl, in aqueous solution was investigated and on increasing 12 25 2 temperature, a morphological transformation from bilayer sheet to spherical micelles was observed and a large hysteresis

Download or read book Photophysical and Liquid Crystalline Properties platinum II Complexes and Luminescent Properties of Third row Metal Complex written by 王康為 and published by . This book was released on 2009 with total page 172 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Design Structures Spectroscopic and Photophysical Properties of Supramoleculsar Gold i Platinum ii and Palladium ii Complexes written by 曾炳堯 and published by . This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Structures, Spectroscopic, and Photophysical Properties of Supramoleculsar Gold(I), Platinum(II), and Palladium(II) Complexes" by 曾炳堯, Biing-chiau, Tzeng, 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. DOI: 10.5353/th_b3123778 Subjects: Gold Platinum Palladium Complex compounds

Download or read book Self assembly of Two and Three dimensional Palladium II and Platinum II Macrocyclic Complexes written by Jun Fan and published by . This book was released on 1999 with total page 830 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Syntheses Characterization and Photophysical Properties of Platinum II and Gold I Complexes Containing Ortho and Meta oligo phenyleneethynylene Ligands written by Mingxin Zhu and published by . This book was released on 2008 with total page 366 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Click Polymerization written by Anjun Qin and published by Royal Society of Chemistry. This book was released on 2018-08-28 with total page 260 pages. Available in PDF, EPUB and Kindle. Book excerpt: Click Polymerization has been edited by world renowned experts and provides an authoritative guide to this reaction type.