Download or read book Design and Synthesis of Functionalized Alkynylplatinum II Polypyridyl Complexes and Oligothienylenevinylene Derivatives written by Chi-Ho Kwok 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 Functionalized Alkynylplatinum (II) Polypyridyl Complexes and Oligothienylenevinylene Derivatives: From Dye-sensitized Solar Cells to Bilayer Heterojunction Photovoltaics" by Chi-ho, Kwok, 郭志豪, 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 alkynylplatinum(II) polypyridine complexes with 4,4′,4′′-tricarboxy-2,2′ 6′,2′′-terpyridine and 4,4′-dicarboxy-2,2′-bipyridine as TiO2 anchoring functionalities, has been successfully synthesized. Their photophysical, electrochemical and luminescence properties have been extensively studied. The excited state properties were probed using nanosecond transient absorption spectroscopy. [Pt(tctpy)(C≡C-Th-BTD-Th)][NnBu4]2 displayed a long-lived transient signal which was tentatively assigned to result from the formation of a charge-separated state, which could be alternatively described as a [Pt(tctpy) (C≡C-Th-BTD-Th)]?] state, with the charge recombination rate constant determined to be 2.9 105 s?1. The excited state redox potentials for the oxidation process were determined and the data confirmed the ability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, which have been characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm-2). A new class of molecular dyads comprising metalloporphyrin-linked alkynylplatinum(II) polypyridine complexes was synthesized and characterized. Their photophysical, electrochemical and luminescence properties have been studied in detail. The excited state properties were probed using nanosecond transient absorption spectroscopy which indicated the formation of a charge-separated state involving the porphyrin radical anion, [Por －(C≡C)Pt]?]. The excited state redox potentials for the oxidation process were also determined with the data supporting the capability of the complexes to inject an electron into the conduction band of TiO2. The majority of the complexes were found to sensitize the nanocrystalline TiO2 and exhibit photovoltaic properties, as characterized by current-voltage measurements under illumination of air mass (AM) 1.5G sunlight (100 mW cm-2). A series of organic materials consisting of a triphenylamine-based donor with oligothiophene or oligothienylenevinylene based-conjugated linker and dicyanovinyl, tricyanovinyl or cyanacrylic acid groups as acceptor, was synthesized and characterized. Their photophysical, electrochemical, thermal and luminescence properties were studied. Transient absorption spectra of TPA-OTV-DCN in dichloromethane solution on the pico- to nanosecond timescale were recorded after femtosecond laser excitation at 400 nm. A transient signal at ca. 700 nm was tentatively assigned to result from the formation of a charge-separated [(TPA-OTV)] DCN ] state with the charge recombination rate constant determined to be 5.3 109 s?1. The energy levels of the LUMOs of TPA-OTV1-DCN, TPA-OTV2-DCN, TPA-OTV3-DCN TPA-TAZ1-DCN, TPA-TAZ2-DCN and TPA-o-4Th-DCN were calculated to be of ca. ?3.9 eV, establishing the formation of a downhill driving force for the energetically favorable electron transfer process involvi
Download or read book Design and Synthesis of Functionalized Alkynylplatinum II Polypyridyl Complexes and Oligothienylenevinylene Derivatives written by Chi-ho Kwok (Ph. D.) and published by . This book was released on 2012 with total page 389 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Design and Synthesis of Functionalized Alkynylplatinum II Polypyridyl Complexes and Oligothienylenevinylene Derivatives written by 郭志豪 and published by . This book was released on 2012 with total page 389 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book DESIGN SYNTHESIS FUNCTIONALI written by Yu-Lut Leung and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 336 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis and Functionalization of Luminescent Alkynylplatinum(II) Complexes of Tridentate N-donor Ligands as Building Blocks for Metallofoldamers, Supramolecular Assemblies and Nanostructures" by Yu-lut, Leung, 梁宇律, 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 FUNCTIONALIZATION OF LUMINESCENT ALKYNYLPLATINUM(II) COMPLEXES OF TRIDENTATE N-DONOR LIGANDS AS BUILDING BLOCKS FOR METALLOFOLDAMERS, SUPRAMOLECULAR ASSEMBLIES AND NANOSTRUCTURES submitted by LEUNG Yu Lut Sammual for the degree of Doctor of Philosophy at The University of Hong Kong in August 2013 A series of dinuclear platinum(II)-containing meta-phenylene ethynylene (mPE) oligomers and binaphthol derivatives of various lengths, end-capped with symmetric or unsymmetric platinum(II) terpyridine units has been synthesized and characterized. In addition, a mononuclear complex with five repeating mPE units has also been synthesized for comparison studies. Dinuclear alkynylplatinum(II) terpyridine complexes with the optimum length of meta-phenylene ethynylene (mPE) units and the binaphthol derivatives have been found to exhibit a strong tendency to fold back onto themselves to form short helical strands through the stabilization of Pt---Pt and interactions. The steric bulk of the terpyridine ligands and the length of the oligomeric bridge have been found to affect the extent of the intramolecular Pt---Pt interaction that governs the i stabilization of the short helical strand in solution. Their folding properties via Pt---Pt and stacking interactions have been studied by H NMR, 2D ROESY NMR, electronic absorption, circular dichroism and emission spectroscopies. A series of dinuclear alkynylplatinum(II) terpyridine complexes bridged by the amphiphilic binaphthol backbone bearing two triethylene glycol monomethyl ether (TEG) chains has been synthesized and characterized. Particularly, one of the complexes with the optimum length of the binaphthol derivative has been shown to undergo transverse aggregation arising from the intra- and intermolecular Pt---Pt and stacking interactions in aqueous solutions. Such hierarchical assembly of helical strands into tubular columns has been studied by electronic absorption, circular dichroism, and emission spectroscopies, as well as electron microscopies. On the other hand, a series of dinuclear alkynylplatinum(II) terpyridine complexes based on the amphiphilic oligo(para-phenylene ethynylene) (OPE) moiety has been synthesized and characterized. Some of the complexes have been shown to self-assemble into various nanostructures from helical fibers to nanotubes, which have been observed in electron microscopies. The supramolecular polymerization process that occurs through non- covalent Pt---Pt and stacking interactions during self-assembly has also been studied by the NMR and UV-vis absorption spectroscopies. A series of alkynylplatinum(II) complexes with a tridentate pyridine-based N- heterocyclic carbene 2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) ligand, II [Pt (C DEGREESN DEGREESC)(CCR)](PF ), and their chloroplatinum(II) precursor complex, II [Pt (C DEGREESN DEGREESC)Cl)](PF ) have been synthesized and characterized. One of the alkynylplatinum(II) complexes has also been structurally characterized by X-ray ii crystallography. Their electrochemistry, electronic absorption and luminescence properties have been studied. Nanosecond transient absorption (TA) spectroscopy has also been performed to probe the nature of the excited state.
Download or read book DESIGN SYNTHESIS FUNCTIONALI written by Yiu-Yan Tam and published by Open Dissertation Press. This book was released on 2017-01-24 with total page 334 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design, Synthesis and Functionalization of Luminescent Alkynylplatinum(II) Complexes of Tridentate N-donor Ligands as Building Blocks for Metallogelation and Supramolecular Assembly" by Yiu-yan, Tam, 譚耀欣, 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_b4322384 Subjects: Complex compounds - Synthesis Platinum compounds - Synthesis Photochemistry Ligands Colloids
Download or read book Design Synthesis and Functionalization of Alkynylplatinum II Complexes with Tridentate N donor Ligands written by 房詩詩 and published by . This book was released on 2020 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Design and Synthesis of Luminescent Alkynylplatinum II Terpyridine Complexes and Their Function As Optical Probes for Biomolecules and Ions written by Ching-Lam Margaret Yeung 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 and Synthesis of Luminescent Alkynylplatinum (II) Terpyridine Complexes and Their Function as Optical Probes for Biomolecules and Ions: From Self-aggregarion, Supramolecular Assembly to Host-guest Chemistry" by Ching-lam, Margaret, Yeung, 楊靖琳, 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 number of cationic water-soluble alkynylplatinum(II) terpyridine complexes, [Pt(tpy){C≡CCH2OC6H3-(CH2OH)2-3,5}]OTf, [Pt(tBu3tpy){C≡CCH2OC6H3- (CH2OH)2-3,5}]Cl, [Pt(tpy){C≡CCH2OC6H4-(CH2OH)-4}]OTf, [Pt(tpy){C≡CC6H3- (CH2OH)2-3,5}]OTf, [Pt(tpy){C≡CC6H4-(CH2OH)-4}]OTf, [Pt(tpy)(C≡C－C≡CH)]OTf and [Pt(tpy){C≡CC6H4(CH2NMe3)-4}](OTf)2, have been synthesized. Phosphate anion derivatives of polyanionic nature, e.g. adenosine triphosphate and tyrosine-containing phosphopeptide, were employed to investigate the induced supramolecular helical assembly behaviors of several of the water-soluble platinum(II) complexes through the study of their UV-vis absorption, emission and circular dichroism (CD) spectroscopies. The extent of such induced self-aggregation properties has been shown to be dependent on the concentration of substrates and capable of screening their respective structurally similar analogues. Two of the complexes were further explored for their use as label-free detection probes for real-time monitoring of the conversion of these phosphate anion derivatives to their metabolic products catalyzed by several biologically important enzymes. Michaelis-Menten analyses have been performed to determine the kinetic parameters. Supramolecular self-assembly and disassembly behaviors of water-soluble platinum(II) complexes have also been explored for their sensing applications for biomacromolecules with quantitative analyses based on UV-vis, emission and CD spectral titration studies. Making use of the selective binding affinity of aptamers towards their target substrates, the extent of self-assembly of the platinum(II) complexes in the presence of lysozyme and thrombin, which arose from their electrostatic interactions with the negatively charged aptamers, could be modulated for the quantification of these substrates. The potential applicability of this probing strategy in real biological environment has been assessed. Other than that, CD spectroscopic studies revealed the formation of supramolecular helical assembly of the platinum(II) complexes upon electrostatic interaction with heparin. Such helical conformation of the heparin-complex mixture together with the distribution of the negatively charged functionalities on the heparin have endowed the complex with high differentiating power for screening possible interfering analogues. Insulin has also been employed as a template for inducing the self-assembly of the platinum(II) complex. Changes in negative surface charge distribution on insulin, brought about by its conformational changes upon conversion to insulin amyloid under destabilizing conditions, have resulted in different extent of induced self-assembly of the metal complex. Spectral changes of the platinum(II) complex has provided a convenient monitoring of insulin amyloid formation, with kinetic parameters determined. A number of platinum(II) complexes with nucleobase-functionalized alkynyl ligands, [Pt(tpy)(C≡CCH2-T-1)]OTf, [Pt(tBu3tpy)(C≡CCH2T-1)]OTf, [Pt(tpy)(C≡C- CH2-A-9)]OTf, [Pt(tpy)(C≡CCH2-C-1)]OTf and [Pt(tpy)(C≡CCH2-G-9)]OTf (T = thymine; A = adenine; C = cytosine; and G = guanine), and amide-functionalized terpyridine ligands, [Pt{tpy-(CONHPh)2}(C≡CPh)]PF6 and [Pt{tpy-(CONHC6H13)
Download or read book Design Synthesis and Functionalization of Luminescent Alkynylplatinum II Complexes of Tridentate N donor Ligands as Building Blocks for Metallofoldamers Supramolecular Assemblies and Nanostructures written by 梁宇律 and published by . This book was released on 2013 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Design Synthesis and Functionalization of Luminescent Alkynylplatinum II Complexes of Tridentate N donor Ligands as Building Blocks for Metallogelation and Supramolecular Assembly written by Yiu-yan Tam and published by . This book was released on 2009 with total page 628 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Transition Metal and Rare Earth Compounds III written by Hartmut Yersin and published by Springer Science & Business Media. This book was released on 2004-11-18 with total page 312 pages. Available in PDF, EPUB and Kindle. Book excerpt: With contribution by numerous experts
