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Light Emitting Platinum Ii And Gold I Complexes Containing Alkynyl And Isocyanide Ligands
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Book Synopsis Light-emitting Platinum (II) and Gold (I) Complexes Containing Alkynyl and Isocyanide Ligands by : Lok-fung Chow
Download or read book Light-emitting Platinum (II) and Gold (I) Complexes Containing Alkynyl and Isocyanide Ligands written by Lok-fung Chow and published by . This book was released on 2010 with total page 460 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Light-Emitting Platinum (II) and Gold (I) Complexes Containing Alkynyl and Isocyanide Ligands by : Lok-Fung Chow
Download or read book Light-Emitting Platinum (II) and Gold (I) Complexes Containing Alkynyl and Isocyanide Ligands written by Lok-Fung Chow and published by . This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Platinum(ii), Palladium(ii) and Gold(iii) Complexes Containing Isocyanide, Alkynyl and N-Heterocyclic Carbene Ligands by : Faan-Fung Hung
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 (0.650.01, 0.350.01) 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)(CCPh)](〖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)(CCPh)]+ (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 &
Book Synopsis LIGHT-EMITTING PLATINUM (II) & by : Wei Lu
Download or read book LIGHT-EMITTING PLATINUM (II) & written by Wei Lu and published by Open Dissertation Press. This book was released on 2017-01-28 with total page 324 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Light-emitting Platinum (II) and Gold (I) Complexes Containing Cyclometalated and Alkynyl Ligands" by Wei, Lu, 陸為, 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 LIGHT-EMITTING PLATINUM(II) AND GOLD(I) COMPLEXES CONTAINING CYCLOMETALATED AND ALKYNYL LIGANDS Submitted by Lu Wei for the degree of Doctor of Philosophy at The University of Hong Kong in July 2003 The syntheses, characterizations, spectroscopic properties and applications of light-emitting platinum(II) and gold(I) complexes containing cyclometalated and alkynyl ligands are described and five systems are explored in detail. The tuning of the photoluminescent properties of tridentate cyclometalated platinum(II) complexes bearing σ-alkynyl auxiliaries, namely [(C DEGREESN DEGREESN)Pt(C≡C) R] [H(C DEGREESN DEGREESN) = 6-aryl- 2,2'-bipyridine; n = 1-4; R = aryl, alkyl or trimethylsilyl], through modifications of both the cyclometalating and acetylide ligands, is presented. These neutral Pt(II) materials exhibit enhanced stability during vacuum deposition. Organic light-emitting devices (OLEDs) based on these emitters display orange to red electrophosphorescence with low turn-on voltages ( 4 V), maximum luminance -2 -1 approaching 10,000 cd m and efficiencies up to 4.2 cd A . The crystal structures and photoluminescence of tethered trinuclear cyclometalated platinum(II) complexes, 3+ namely [{R(C DEGREESN DEGREESN)} Pt ( -dpmp)] (R denotes substituent(s) on the (C DEGREESN DEGREESN) 3 3 3 ligand, dpmp = bis(diphenylphosphinomethyl)phenylphosphine), were investigated and compared with their mono- and binuclear analogues to yield insight into the nature of their respective excited states. The emission energies were found to be dependent on the substituents on the cyclometalating ligands and the oligophosphine 8 8 ligands, and sensitive to d -d and π-π interactions. Intermolecular π-stacking interactions were found to affect the crystal packing, solid-state emission energy and vapochromic behavior of mono- and multinuclear dicyclometalated Pt(II) complexes, 1 1 namely [Pt(C DEGREESN DEGREESC)L ] [HC DEGREESN DEGREESCH = 2,6-diphenylpyridine; L = pyridine, isocyanide, 2 2 phosphine], [Pt (C DEGREESN DEGREESC) (-L )] [L = pyrazine, bidentate phosphine] and 2 2 [Pt (C DEGREESN DEGREESC) ( -dpmp)], and aromatic α-diimine Pt(II) complexes bearing 3 3 3 t t functionalized σ-alkynyl auxiliaries, namely [( Bu bpy)Pt(C≡CAr) ] ( Bu bpy = 4,4'- 2 2 2 bis-tert-butyl-2,2'-bipyridine, Ar = 4-pyridyl, 3-pyridyl, 2-pyridyl, 4-ethynylpyridyl, 2-thienyl and pentafluorophenyl). The weak non-covalent interactions observed in the solvated crystal structures, such as π-π, C-H---π(C≡C), C-H---N(py), C-H---F-C and Cl---Cl contacts, were invoked to rationalize the reversible VOC (volatile organic compound) sensing and signaling capabilities of these materials. The syntheses, crystal structures and spectroscopic properties of several π-conjugated carbon-rich scaffolds bearing [Au(PCy )] (Cy = cyclohexyl) termini are described. The ν of the 3 0-0 acetylenic (ππ*) emission for [(Cy P)Au(C≡C) Au(PCy )] (n = ∞) was estimated to 3 n 3 -1 1 occur at 11000 cm by extrapolation of the plot of ν versus 1/n. Prompt (ππ*) 0-0 fluorescence only was detected from the cross-conjugated species [TEE][Au(PCy )] 3 4 ([TEE]H = tetraethynylethene). A correlation between the solid-state emissions and crystal structures of the phosphorescent polymorphic complex [4-NO - C H C≡CAu(PCy )] and their related complexes was observed, and a rationale based 6 4 3 on excitonic coupling is proposed. DOI: 10.5353/th_b
Book Synopsis Luminescent Platinum(II), Palladium(II) and Gold(III) Complexes Containing Isocyanide, Alkynyl and N-heterocyclic Carbene Ligands by : 孔繁峰
Download or read book Luminescent Platinum(II), Palladium(II) and Gold(III) Complexes Containing Isocyanide, Alkynyl and N-heterocyclic Carbene Ligands written by 孔繁峰 and published by . This book was released on 2014 with total page 580 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Light-Emitting Platinum (II) and Gold (I) Complexes Containing Cyclometalated and Alkynyl Ligands by : WEI. LU
Download or read book Light-Emitting Platinum (II) and Gold (I) Complexes Containing Cyclometalated and Alkynyl Ligands written by WEI. LU and published by . This book was released on 2017-01-28 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Light-emitting Platinum (II) and Gold (I) Complexes Containing Cyclometalated and Alkynyl Ligands by : Wei Lu (Ph.D.)
Download or read book Light-emitting Platinum (II) and Gold (I) Complexes Containing Cyclometalated and Alkynyl Ligands written by Wei Lu (Ph.D.) and published by . This book was released on 2003 with total page 648 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Platinum(II), Gold(I) and Gold(III) Complexes Containing Allenylidene And/or Isocyanide Ligands by : 肖欣珊
Download or read book Luminescent Platinum(II), Gold(I) and Gold(III) Complexes Containing Allenylidene And/or Isocyanide Ligands written by 肖欣珊 and published by . This book was released on 2015 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Platinum(ii) Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen, Nitrogen and Carbon Donor Atoms and Platinum(ii)-Containing Phosphorescent Polymers by : Wai-Yip Tong
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
Book Synopsis DESIGN & SYNTHESIS OF LUMINESC by : Suk-Hang Lam
Download or read book DESIGN & SYNTHESIS OF LUMINESC written by Suk-Hang Lam and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 292 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design and Synthesis of Luminescent Platinum(II) and Gold(III) Complexes With Tridentate Pincer-type Ligands: From Computational Study to Experiments and Application Studies" by Suk-hang, Lam, 林淑恒, 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 PLATINUM(II) AND GOLD(III) COMPLEXES WITH TRIDENTATE PINCER-TYPE LIGANDS - FROM COMPUTATIONAL STUDY TO EXPERIMENTS AND APPLICATION STUDIES Submitted by LAM Suk Hang for the degree of Doctor of Philosophy at The University of Hong Kong in June 2015 Square planar platinum(II) and gold(III) complexes possess unique spectroscopic and photophysical properties which enable them as promising candidates for many applications such as optoelectronic devices and biological sensors. The understanding of the intrinsic properties of these complexes is therefore essential to optimize their performance as well as provide guidance on the molecular design for specific applications. This thesis aims to provide useful insights for the molecular design strategies with the aid of computational studies to tune the electronic properties of these complexes and electroluminescence studies in the fabrication of organic light-emitting devices (OLEDs). Computational studies have been performed to inspect electronic structures and photophysical properties as well as their correlation with the nature of ancillary ligands in the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene, [Pt(bzimb)(C≡C-R)], 1,3-bis-hetero-azolylbenzenes, [Pt(N DEGREESC DEGREESN)(C≡C-R)], and pyridine-based N-heterocyclic carbene, [Pt(NHC)(C≡C-R)] . It was found that the emission of the arylalkynylplatinum(II) complexes with pyridine-based N-heterocyclic carbene ligand was originated from the triplet alkynyl-to-tridentate pincer ligand-to-ligand charge transfer excited state mixed with platinum-to-tridentate pincer metal-to-ligand charge transfer character, and the excited state energy was found to be red-shifted according to the increasing π electron-donating ability of the aryl group attached to the alkynyl ligand. On the other hand, the emission energies of the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene and 1,3-bis-hetero-azolylbenzenes were found to be dependent on the different electron-donating substituents on the pincer ligands. Calculations have also been performed on the representative alkynylplatinum(II) + + complexes [Pt(trpy)(C≡C-R)] (trpy = 2,2′ 6′,2′′-terpyridine), [Pt(bzimpy)(C≡C-R)] (bzimpy = 2,6-bis(N-alkylbenzimidazol-2′-yl)pyridine) and [Pt(bzimb)(C≡C-R)] as well as alkynylgold(III) complexes [Au(C DEGREESN DEGREESC)(C≡C-R)] (C DEGREESN DEGREESC = 2,6-diphenylpyridine), [Au{C(Np) DEGREESN DEGREESC(Np)}(C≡C-R)] (C(Np) DEGREESN DEGREESC(Np) = 2,6-di(2-naphthyl)pyridine) and [Au(N DEGREESN DEGREESN)(C≡C-R)] (N DEGREESN DEGREESN = 2,6-bis(1H-benzimidazol-2-yl)pyridine) in order to have a better understanding on their nature of the emissive origins as well as the radiative and nonradiative processes. In particular, factors governing the ordering of the triplet excited states and radiative decay rate constants of the emissive state ( ES) have been examined. Their potential energy profiles for the deactivation process from the ES via triplet metal-centered states have also been explored. This study revealed for the first time the potential energy profiles for the thermal deactivation pathway of square planar platinum(II) and gold(III) complexes. In addition to the computational
Book Synopsis Luminescent Cyclometalated Gold (III) Complexes with Ancillary N-Heterocyclic Carbene and Alkynyl Ligands by : Ka-Man Au
Download or read book Luminescent Cyclometalated Gold (III) Complexes with Ancillary N-Heterocyclic Carbene and Alkynyl Ligands written by Ka-Man Au 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 Cyclometalated Gold (III) Complexes With Ancillary N-heterocyclic Carbene and Alkynyl Ligands: From Design, Synthesis, Photophysics to Supramolecular Assembly and Functions" by Ka-man, Au, 區嘉雯, 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 library of luminescent cyclometalated gold(III) complexes containing various bis-cyclometalating R-C DEGREESN DEGREESC ligands derived from 2,6-diphenylpyridine and ancillary alkynyl ligands, [Au(R-C DEGREESN DEGREESC)(C≡CR')], has been synthesized. Some of the complexes have been structurally determined by X-ray crystallography. These complexes were found to exhibit intense emission in dichloromethane solution at 298 K, originating from metal-perturbed triplet intraligand (IL) excited states of the R-C DEGREESN DEGREESC ligand, with substantial charge transfer character from the aryl moiety to the pyridyl ring. In the presence of electron-rich alkynyl ligands, the emission origin could be switched to an alkynyl-to-cyclometalating ligand ligand-to-ligand charge transfer (LLCT) excited state. This class of complexes was also demonstrated to show rich electroluminescence properties as emitters in organic light-emitting devices. In addition, the supramolecular assembly of this class of complexes has also been revealed in gelation studies. N-Heterocyclic carbenes have been incorporated into the gold(III) metal center to prepare a series of luminescent mononuclear and dinuclear gold(III) complexes, [{Au(C DEGREESN DEGREESC)}n(NHC)](PF6)n and [{Au(tBuC DEGREESN DEGREESCtBu)}n(NHC)]- (PF6)n (n = 1, 2). The X-ray crystal structures of most of the complexes have been determined. The emissions of these complexes were assigned to originate from the metal-perturbed intraligand excited state of the bis-cyclometalating ligand. One of the C2-bridged dinuclear complexes was found to exhibit two distinct reduction couples, tentatively correlated to the presence of significant intramolecular π-π interaction in the complex. Two novel series of luminescent mononuclear alkynylgold(III) complexes, [Au(C DEGREESN)(C≡CR)2] (HC DEGREESN = 2-phenylpyridine (Hppy) and derivatives) and [Au(C DEGREESN DEGREESN)(C≡CR)]PF6 (HC DEGREESN DEGREESN = 6-phenyl-2,2'-bipyridine and derivatives), have been synthesized. Some of the X-ray crystal structures have been determined. The former class of complexes with bidentate C DEGREESN ligands has been observed to show tunable emission spanning across the visible spectrum from 462 to 697 nm. With the exception of [Au(ppy)(C≡C-C6H4-NH2-p)2] which showed a low-energy band originated from a 3LLCT [π(C≡C-C6H4-NH2)→π*(C DEGREESN)] excited state, all complexes exhibited vibronic-structured emission bands originated from the intraligand transition of the cyclometalating C DEGREESN ligand in dichloromethane solution at 298 K. On the other hand, most of the complexes with the tridentate C DEGREESN DEGREESN-type ligand have been observed to exhibit vibronic-structured emission bands attributed to the intraligand transition of the C DEGREESN DEGREESN ligand in low-temperature butyronitrile glass. DOI: 10.5353/th_b4775268 Subjects: Organogold compounds - Synthesis Carbenes (Methylene compounds) Heterocyclic compo
Book Synopsis Syntheses, Characterization and Photophysical Properties of Platinum(ii) and Gold(i) Complexes Containing Ortho- And Meta-Oligo(phenyleneethynylene) Ligands by : 朱明新
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
Book Synopsis Photoluminescent and Electroluminescent Properties of Neutral Platinum (II) Complexes Containing Alkynyl and Multi-Anionic Ligands by : Siu-Chung Chan
Download or read book Photoluminescent and Electroluminescent Properties of Neutral Platinum (II) Complexes Containing Alkynyl and Multi-Anionic Ligands written by Siu-Chung Chan and published by . This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Functionalized Platinum (II) and Gold (I) Acetylide Complexes by : Yuen-Ting Shum
Download or read book Functionalized Platinum (II) and Gold (I) Acetylide Complexes written by Yuen-Ting Shum 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, "Functionalized Platinum (II) and Gold (I) Acetylide Complexes: Structural and Spectroscopic Properties and Anticancer Activities" by Yuen-ting, Shum, 岑婉婷, 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 FUNCTIONALIZED PLATINUM(II) AND GOLD(I) ACETYLIDE COMPLEXES. STRUCTURAL AND SPECTROSCOPIC PROPERTIES AND ANTICANCER ACTIVITIES Submitted by SHUM YUEN TING For the degree of Doctor of Philosophy at The University of Hong Kong in April 2007 Planar [Pt(terpy)X] complexes (terpy = 2,2':6',2''-terpyridine; X = Cl, SR) have frequently been cited as classic DNA metallointercalators in bioinorganic chemistry; + however, application studies of [Pt(terpy)L] (L = monoanionic ligand) and its derivatives in metal-based therapeutics are limited. In this work, a series of platinum(II) terpyridine complexes containing different glycosylated acetylide and arylacetylide ligands were prepared and characterized, the photophysical properties of which were investigated. A low-energy absorption band at 409-476 nm, which was assignable to a MLCT transition was observed in its electronic absorption spectra. Upon photoexcitation, intense emission bands at 513-733 nm were observed and were believed to originate from the excited states of 3 3 MLCT and LLCT character. Cytotoxic activities of the ''Pt(terpy)(glycosylated arylacetylide)'' system with significant inhibitory effect toward a series of carcinoma cell lines were discovered. [Pt( Bu terpy)(L3)](CF SO ) (L3 = 4-ethynylphenoxy 3 3 3 -2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside) (IC = 0.06-0.1 M) was found to be 50 i260-fold more effective in growth inhibition of the human brain cancer cell line (SF-268) than cisplatin. The binding interactions of selected platinum(II) complexes 4 5 -1 3 to calf-thymus DNA featured binding constants of 10-10 mol dm . Significantly, the spectral data were found to support a specific binding mode at the AT sequences of DNA for selected complexes. The results of cytometry experiments showed that [Pt( Bu terpy)(L3)](CF SO ) 3 3 3 induce 52.4% apoptosis in NCI-H460 cells. Based on microarray and Western blotting analyses, down-regulation of anti-apoptotic proteins, including Bcl-2 and caspase-3, were observed for platinum-treated NCI-H460 cells. When taken together, the [Pt( Bu terpy)(L3)](CF SO)-induced apoptosis in NCI-H460 cells should 3 3 3 normally occur via the mitochondrial pathway. A family of mono- and binuclear Cy P-supported gold(I) complexes which contained various π-conjugated arylacetylide ligands, were prepared and characterized. The lowest-energy singlet transitions were predominately intraligand in nature and exhibited both phenyl and acetylenic (ππ*) character. The organic triplet emissions of arylacetylide groups were thus "illuminated" at ambient conditions by ligation to the [Au(PCy )] fragment. Strong photoluminescence was detected in solid and solution states of the gold(I) complexes under ambient conditions with lifetimes in the microsecond regime. Selected gold(I) complexes were also subjected to cytotoxicity analysis; only [Au(PCy )(C≡CC H )] showed cytotoxicities (IC = 3 10 7 50 4.9-14.5 M) that were comparable to clinical cisplatin. An acetylide ligand that was appended with lomefloxacin moiety was coordinated to ii with gold(I) and platinum(II) complexes to form [CyPAu(lome)] and [Pt( Bu tpy)(lome)] (CF SO ) (lome = modified lomefloxacin), both of which were 3 3 3 structurally characterized. Tw
Book Synopsis Luminescent Cyclometalated Platinum (II) Complexes with Isocyanide Ligands as Nucleic Acid Probes, Topoisomerase Poisons and Anti-Cancers Agents by : Jia Liu
Download or read book Luminescent Cyclometalated Platinum (II) Complexes with Isocyanide Ligands as Nucleic Acid Probes, Topoisomerase Poisons and Anti-Cancers Agents written by Jia Liu 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 Cyclometalated Platinum (II) Complexes With Isocyanide Ligands as Nucleic Acid Probes, Topoisomerase Poisons and Anti-cancers Agents" by Jia, Liu, 刘佳, 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: LUMINESCENT CYCLOMETALATED PLATINUM (II) COMPLEXES WITH ISOCYANIDE LIGANDS AS NUCLEIC ACID PROBES, TOPOISOMERASE POISONS AND ANTI-CANCER AGENTS LIU JIA Ph.D. THESIS THE UNIVERSITY OF HONG KONG May 2011 Abstract of thesis entitled LUMINESCENT CYCLOMETALATED PLATINUM (II) COMPLEXES WITH ISOCYANIDE LIGANDS AS NUCLEIC ACID PROBES, TOPOISOMERASE POISONS AND ANTI-CANCER AGENTS Submitted by Liu Jia for the degree of Doctor of Philosophy at The University of Hong Kong in May 2011 Since the discovery of anti-cancer cisplatin and its derivatives, extensive studies have been conducted on the interaction between platinum(II) complexes and their proposed cellular target DNA. Besides DNA, other cellular targets which may improve cancer cell specificity are less explored. Recent studies have shown that poisoning of DNA topoisomerases (Topo) could be owing to DNA interaction by DNA intercalators. In this thesis work, a class of planar cyclometalated platinum(II) complexes were prepared and their activities on DNA and Topo were examined. A new class of highly cytotoxic luminescent platinum(II) complexes containing C DEGREESN DEGREESN (HC DEGREESN DEGREESN = 6- phenyl-2,2′-bipyridine) ligand were prepared and found to II act as DNA TopoI poisons and probes. [Pt (C DEGREESN DEGREESN)(C≡NR)]ClO 3-1c (R = tert-butyl) inhibited TopoI-mediated DNA relaxation with concentration down to 20 nM. The high potency of 3-1c towards TopoI was attributed to its stabilization of the transient TopoI-DNA cleavage complexes via π---π interactions. The superior photoluminescent properties of 3-1c were used for the in-gel detection of TopoI-DNA cleavage complexes. The detection limit of this method was determined to be approximately 1.8 U/L, which is similar to that of western blotting (1.2 U/L) and much lower than that of coomassie blue staining. 3-1c displayed a significantly high cytotoxicity against human carcinoma cell lines while relatively low toxicity toward normal human cells. The cell death pathway caused by 3-1c was attributed to its TopoI poisoning, which induces cell cycle arrest and apoptosis. Another series of platinum(II) complexes which contain bidentate C DEGREESN ligands II were prepared. [Pt (C DEGREESN)(C≡NR) ]OTf 4-1d (HC DEGREESN = 2-phenylpyridine, R = 2-naphthyl) is stable under physiological conditions and intercalates DNA preferentially at major groove. This complex inhibits TopoIIα-mediated DNA relaxation and kDNA decatenation, with a much higher potency than the known TopoIIα poison Vp-16. To confirm that the cytotoxicity of 4-1d is related to its TopoIIa poisoning, wild-type and TopoIIa-knockdown SUNE1 cell lines were established using siRNA method. Compared with the parental cells, 4-1d is 22-fold less cytotoxic towards the cells with reduced TopoIIa expression, suggesting that TopoIIa is a cellular target of 4-1d. Self-assembling properties of the cyclometalated platinum(II) complexes on phosphate backbones of oligonucleotides due to electrostatic interaction were studied. Due to the superior photophysical properties of the platinum(II) complexes, the subtle competition between self-assembling and hydrophobic intercalation of platinum(II) complexes with DNA can be used to monitor the changes
Book Synopsis Photoluminescent and Electroluminescent Properties of Neutral Platinum (II) Complexes Containing Alkynyl and Multi-anionic Ligands by : Siu-chung Chan (Ph.D.)
Download or read book Photoluminescent and Electroluminescent Properties of Neutral Platinum (II) Complexes Containing Alkynyl and Multi-anionic Ligands written by Siu-chung Chan (Ph.D.) and published by . This book was released on 2004 with total page 548 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis DESIGN SYNTHESIS & FUNCTIONALI by : Yau-Hin Hong
Download or read book DESIGN SYNTHESIS & FUNCTIONALI written by Yau-Hin Hong and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 332 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis and Functionalization of Luminescent Alkynylgold(I) Complexes With [pi]-conjugated Ligands: From Photophysics to Supramolecular Assembly" by Yau-hin, Hong, 康祐軒, 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 the thesis entitled DESIGN, SYNTHESIS AND FUNCTIONALIZATION OF LUMINESCENT ALKYNYLGOLD(I) COMPLEXES WITH π-CONJUGATED LIGANDS FROM PHOTOPHYSICS TO SUPRAMOLECULAR ASSEMBLY Submitted by HONG Yau Hin for the Degree of Doctor of Philosophy at The University of Hong Kong in July 2015 A library of polynuclear thiophene-based alkynylgold(I) complexes with N-heterocyclic carbenes (NHCs) and triphenylphosphine as the peripheral ligands, [R{(C≡C)Au(NHC)} ] (R = benzo[1,2-b:4,5-b']dithiophene, n = 2, 4; benzo[1,2- b:3,4-b':5,6-b'']trithiophene, n = 3; dithieno[3,2-b:2',3'-d]thiophene, n = 2; dithieno[3,2-e:2',3'-g](dibenzo[b, d]-thiophene), n = 2; 4-hexyl-4H-dithieno[3,2- b:2',3'-d]pyrrole, n = 4) and [R'{(C≡C)Au(PPh )}] (R' = benzo[1,2-b:4,5- 3 2 b']dithiophene), has been synthesized and characterized. The X-ray crystal structure of [BDT{(C≡C)Au(IHex)} -2,6] (BDT = benzo[1,2-b:4,5-b']dithiophene, IHex = 1,3-dihexylimidazol-2-ylidene) has been determined by X-ray crystallography. This class of complexes showed dual emissive behaviour and exhibited broad vibronic-structured emission bands in degassed dichloromethane solution at ambient temperature. As demonstrated by the temperature-dependent UV-vis absorption spectroscopy, some of the alkynylgold(I) complexes were shown to self-assemble in THFwater mixtures through a cooperative growth mechanism. Variation of the alkyl chain length on the NHC ligands not only has a significant effect on the morphologies of the aggregates, but also on the thermodynamic parameters of the self-assembly processes as revealed by the nucleationelongation model. Apart from the thiophene-based sulfur heterocycle-containing alkynylgold(I) system, a series of N-alkyl substituted triindole-based nitrogen heterocycle-containing trinuclear alkynylgold(I) complexes with isocyanide and NHCs as the peripheral ligands, [(TATI){(C≡C)Au(C≡N-R)}] (TATI = trialkyltriindole; R = 2,6-dimethoxyphenyl, 2,6-dimethylphenyl), and [(TATI){(C≡C)Au(NHC)}], has been prepared and characterized. The photophysical properties of the trinuclear alkynylgold(I) complexes have been examined. Their self-assembly properties have also been explored using TEM, SEM, DLS, H NMR spectroscopy, solvent-dependent and variable-temperature UV-vis absorption experiments. Some of the complexes have been demonstrated to possess spherical nanostructures in their THFwater dispersions. The self-assembly was believed to be mediated by the ππ stacking interactions of the central triindole moiety and governed by a cooperative growth mechanism. In addition, a novel class of amphiphilic phosphole-based phosphorus heterocycle-containing alkynylgold(I) complexes, [Au(C≡C-R){Ph-DBP(O)- ] O(CH ) SO }]K (DBP = 5H-dibenzophosphole; R = phenyl, naphthyl, 2 3 3 phenanthrenyl, pyrenyl, perylenyl, 4-methoxyphenyl, 4-chlorophenyl) was designed and synthesized. The photophysical properties of this class of complexes have been studied. Some of the complexes were shown to display sheet-like nanostructures in aqueous DMSO solution. The self-assembly process was found to be governed by an isodesmic mechanism and mediated by hydrophobichydrophobic interactions between the alkynyl units. It has been shown that modulation of t
