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Book Luminescent Cyclometalated Platinum II  and Gold III  Complexes for Molecular Recognition and DNA Binding Studies

Download or read book Luminescent Cyclometalated Platinum II and Gold III Complexes for Molecular Recognition and DNA Binding Studies written by Kar-ho Wong and published by . This book was released on 1999 with total page 364 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Luminescent Cyclometalated Platinum  II  Complexes in DNA Binding Studies and Their Cytotoxicities Against Carcinoma Cell Lines

Download or read book Luminescent Cyclometalated Platinum II Complexes in DNA Binding Studies and Their Cytotoxicities Against Carcinoma Cell Lines written by Dik-Lung Edmond Ma 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 in DNA Binding Studies and Their Cytotoxicities Against Carcinoma Cell Lines" by Dik-lung, Edmond, Ma, 馬迪龍, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. DOI: 10.5353/th_b3124581 Subjects: Antineoplastic agents Platinum compounds Cancer cells - Genetics Apoptosis

Book Luminescent Cyclometalated Platinum ii  Complexes

Download or read book Luminescent Cyclometalated Platinum ii Complexes written by Kit-Man Phyllis Siu and published by . This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Luminescent Cyclometalated Platinum(II) Complexes: Protein Binding Studies and Biological Applications" by Kit-man, Phyllis, Siu, 蕭潔敏, 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_b4501498 Subjects: Platinum compounds - Synthesis Photoluminescence DNA-ligand interactions

Book Luminescent Cyclometalated Platinum  II  Complexes in DNA Binding Studies and Their Cytotoxicities Against Carcinoma Cell Lines

Download or read book Luminescent Cyclometalated Platinum II Complexes in DNA Binding Studies and Their Cytotoxicities Against Carcinoma Cell Lines written by Dik-lung Ma (Edmond) and published by . This book was released on 2003 with total page 550 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Luminescent Cyclometalated Platinum II  Complexes

Download or read book Luminescent Cyclometalated Platinum II Complexes written by Kit-man Siu (Phyllis) and published by . This book was released on 2005 with total page 576 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book DESIGN   SYNTHESIS OF LUMINESC

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 Synthesis and Characterization of Luminescent Gold III  Complexes

Download or read book Synthesis and Characterization of Luminescent Gold III Complexes written by Amanda N. Sulicz and published by . This book was released on 2017 with total page 264 pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemistry of cyclometalated gold(III) has been relatively slow to emerge, but recent advances in catalyst and material design have driven a renewed interest. Reported here are synthetic, structural, and optical studies of cyclometalated gold(III) aryl complexes. These new complexes show ligand-centered luminescence that is perturbed by the heavy-atom effect of gold. Traditionally, metal-carbon bond formation relied on organometallic complexes of electropositive elements, including lithium and magnesium. The easily reducible nature of gold(III) often interferes with these conventional reagents, thus resulting in the use of toxic metals like mercury or thallium. Reported here is the use of palladium-catalyzed Suzuki-Miyaura cross-coupling for the attachment of aryl ligands to cyclometalated gold(III) chloride complexes. The resulting di- and mono-arylated species were luminescent. Several complexes have been crystallographically characterized. Luminescent derivatives of a previously published gold(III) chloro precursor, initially reported for catalytic purposes, were prepared through boron transmetalation reactions. Complexes bearing both aryl and cyanide ligands were synthesized. These luminescent materials are diamagnetic and were be characterized by multinuclear NMR, absorption and emission spectroscopies (including time-resolved emission), and by X-ray diffraction crystallography. The synthesized gold(I) complexes were designed to display reverse saturable absorption and be a two photon acceptor. The BTF (BTF = 2-(9,9’-diethyl-9H-fluoren-2-yl)-benzothiazole) ligand was chosen as it has been previously demonstrated to have favorable photophysical effects on platinum(II) and ruthenium(II) complexes for applications in photodynamic therapy and optical power limiting (OPL). Gold(I) complexes with the BTF ligand are sought for potential OPL applications. Synthesized complexes are luminescent and were characterized by multinuclear NMR, absorption and emission spectroscopies, photoluminescent quantum yields, time-resolved emission. Two complexes were crystallographically characterized.

Book Luminescent Cyclometalated Gold  III  Complexes with Ancillary N Heterocyclic Carbene and Alkynyl Ligands

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 Luminescent Cyclometalated Platinum  II  Complexes with Isocyanide Ligands as Nucleic Acid Probes  Topoisomerase Poisons and Anti Cancers Agents

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 Luminescent Platinum ii   Palladium ii  and Gold iii  Complexes Containing Isocyanide  Alkynyl and N Heterocyclic Carbene Ligands

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 &

Book Non covalent Interactions  Excited States and Supramolecular Polymerization of Luminescent Cyclometalated D8 Platinum II   Palladium II  and Gold III  Complexes A Combined Theoretical and Experimental Investigations

Download or read book Non covalent Interactions Excited States and Supramolecular Polymerization of Luminescent Cyclometalated D8 Platinum II Palladium II and Gold III Complexes A Combined Theoretical and Experimental Investigations written by 万晴云 and published by . This book was released on 2019 with total page 316 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book LIGHT EMITTING PLATINUM  II

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 Luminescent Platinum ii  Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen  Nitrogen and Carbon Donor Atoms and Platinum ii  Containing Phosphorescent Polymers

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