Download or read book Design and Synthesis of Ligands for Luminescent Metal Complexes written by Tyler Ian Davis and published by . This book was released on 2019 with total page 82 pages. Available in PDF, EPUB and Kindle. Book excerpt: Luminescent metal complexes have been extensively investigated for a wide range of applications, including biological imaging and organic light emitting diodes (OLEDs). The ligand 2,6-bispyrazolepyridine (bppy) has shown itself to be an extremely effective sensitizer for Eu3+ complexes. Derivatives of this ligand have been synthesized with various oxygen containing groups attached at the 4 position of the pyrazoles. A novel diphosphine containing ligand with a terthiophene backbone has been synthesized. It is believed that this ligand could be used in Cu1+ complexes to create electropolymers capable of thermally activated delayed fluorescence (TADF)
Download or read book Design and Synthesis of Luminescent Metal Polypyridyl Complexes of Platinum ii Ruthenium ii and Osmium ii for Chemosensing and Biological Studies written by Wing-Suen Tang 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 Metal Polypyridyl Complexes of Platinum(II), Ruthenium(II) and Osmium(II) for Chemosensing and Biological Studies" by Wing-suen, Tang, 鄧詠璇, 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 METAL POLYPYRIDYL COMPLEXES OF PLATINUM(II), RUTHENIUM(II) AND OSMIUM(II) FOR CHEMOSENSING AND BIOLOGICAL STUDIES Submitted by TANG WING SUEN for the degree of Doctor of Philosophy at The University of Hong Kong in November 2006 A series of platinum(II) terpyridyl alkynyl complexes derivatized with basic amino functionalities and crown ether pendants, [Pt(trpy)(C≡C-R)]X (R = - - -C H -N(CH ) -4, X = OTf; R = -C H -N(CH CH OCH ) -4, X = OTf; R = 6 4 3 2 6 4 2 2 3 2 - - -C H -NH-4, X = OTf; R = -C H -N(CH )-4, X = Cl; R = 6 4 2 6 4 3 2 - - -C H -N(CH CH OCH ) -4, X = Cl; R = -C H -NH -4, X = Cl; R = -B15C5, X 6 4 2 2 3 2 6 4 2 - - = OTf; R = -A15C5, X = OTf ) have been synthesized. The X-ray crystal structure of [Pt(trpy){C≡CC H -N(CH CH OCH )-4}](OTf) has been 6 4 2 2 3 2 determined. The lowest energy absorption of the complexes except [Pt(trpy)(C≡CB15C5)](OTf) were tentatively assigned to originate from a π(C≡C) → π*(trpy) ligand-to-ligand charge transfer (LLCT) transition mixed with some metal-to-ligand charge transfer (MLCT) contribution. The ion-binding and pH dependent properties have also been studied. Their photophysical and spectroscopic properties were shown to be dependent on pH and selected metal ions, and their colorimetric and luminescence chemosensing properties were described. Another series of platinum(II) terpyridyl alkynyl complexes, t - [Pt( Bu trpy)(C≡C-R)]X [R = -C H -NH -4, X = OTf; R = -C H -NCS-4, X = 3 6 4 2 6 4 - - - OTf; R =-C H -NHCOCH I-4, X = OTf; R = -UH-5 (UH = Uracil), X = Cl; 6 4 2 -UMe-5, X = OTf (UMe = 1,3-dimethyluracil)] have been successfully synthesized and characterized. The X-ray crystal structures of t t [Pt( Bu trpy)(C≡C-C H-NCS-4)](OTf), [Pt( Bu trpy)(C≡C-UH-5)]Cl and 3 6 4 3 [Pt( Bu trpy)(C≡C-UMe-5)](OTf) have been determined. Their photophysical and electrochemical behaviour, together with their protein labeling and DNA binding studies, have also been studied. The emission of the complexes in solution at room temperature has been tentatively assigned as originated from a dπ(Pt) → π*( Bu trpy) triplet MLCT excited state. The 77 K butyronitrile glass displayed dual luminescence which were assigned to originate from an intraligand (IL) phosphorescence of the terpyridine ligand and a dπ(Pt) → t 3 t π*( Bu trpy) MLCT phosphorescence. The [Pt( Bu trpy)(C≡C- 3 3 C H-NHCSNH-4)](OTf)-HSA and [Pt( Bu trpy)(C≡C-C H -NHCOCH S- 6 4 3 6 4 2 4)](OTf)-HSA (HSA = human serum albumin) bioconjugates were highly colored and exhibited luminescence in the visible region upon photoexcitation. A series of ruthenium(II) diimine complexes and an osmium(II) diimine complex containing extended π-conjugated ligands, [Ru(bpy) (pmra)](PF ) 2 6 2 [pmra = N-(2-pyridylmethylene)-2-fluorenamine], [Ru(bpy) (pmra)]Cl, 2 2 [Ru(bpy) (pmaa)]Cl [pmaa = N-(2-pyridylmethylene)-2-anthramine], 2 2 [Ru(bpy) (pmpa)]Cl [pmpa = N-(2-pyridylmethylene)-1-pyrenamine], 2 2 [Ru(bpy) (pmfa)]Cl [pmfa = N-(2-pyridylmethylene)-3-fluoranthenamine] 2 2 and [Os(bpy) (pmaa)](PF ), have been synthesized. The lowest energy 2 6 2 absorption bands of the ruthenium(II) complexes w
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
Download or read book Design and Synthesis of Cyclometalated Transition Metal Complexes as Functional Phosphorescent Materials written by Shuang Liu (Ph. D.) and published by . This book was released on 2012 with total page 185 pages. Available in PDF, EPUB and Kindle. Book excerpt: Cyclometalated Ir(III) and Pt(II) compounds are among the most promising phosphorescent emitters for various applications, such as organic light emitting diodes (OLEDs), chemical sensors and bioimaging labels. This family of complexes exhibits high thermal and photo-stability, excellent quantum efficiency, and relatively short lifetime. More importantly, their luminescent properties can be fully tunable by modifying the coordinating ligands. In this thesis, a series of 2-(1,2,3-triazol-4-yl)-pyridine derivatives, referred to as the "click" ligands, are used to build phosphorescent Ir(III) and Pt(II) compounds. The robust and tolerant nature of the copper mediated 1,3-dipolar cycloaddition reactions offers great flexibility in the molecular design. Chapter 1 and Chapter 2 focus on the synthesis of heteroleptic cyclometalated Ir (III) and Pt(II) complexes by utilizing the Cu(I) triazolide intermediates generated in "click" reactions as transmetalating reagents. Ligand synthesis and metalation can be achieved in one pot under mild reaction conditions. For the Ir(III) system, the "click" ligands show switchable coordination modes, between the C, N- and N, N-chelation. These ligands act as C, N, N-bridging units to form unique zwitterionic dinuclear complexes with two cyclometalated Pt(II) units. In Chapter 3, cyclometalated Pt(II) complexes with N, N-chelating "click" ligands are synthesized. Their aggregation-induced solid-state emission is highly responsive to environmental stimuli, such as solvents, heat and mechanical force. This family of compounds represents the first thermotropic Col(h) liquid crystals with only one sidechain. Furthermore, the combined liquid crystalline and mechanochromic properties make them attractive functional materials.
Download or read book Ligand Design in Metal Chemistry written by Mark Stradiotto and published by John Wiley & Sons. This book was released on 2016-09-01 with total page 448 pages. Available in PDF, EPUB and Kindle. Book excerpt: The design of ancillary ligands used to modify the structural and reactivity properties of metal complexes has evolved into a rapidly expanding sub-discipline in inorganic and organometallic chemistry. Ancillary ligand design has figured directly in the discovery of new bonding motifs and stoichiometric reactivity, as well as in the development of new catalytic protocols that have had widespread positive impact on chemical synthesis on benchtop and industrial scales. Ligand Design in Metal Chemistry presents a collection of cutting-edge contributions from leaders in the field of ligand design, encompassing a broad spectrum of ancillary ligand classes and reactivity applications. Topics covered include: Key concepts in ligand design Redox non-innocent ligands Ligands for selective alkene metathesis Ligands in cross-coupling Ligand design in polymerization Ligand design in modern lanthanide chemistry Cooperative metal-ligand reactivity P,N Ligands for enantioselective hydrogenation Spiro-cyclic ligands in asymmetric catalysis This book will be a valuable reference for academic researchers and industry practitioners working in the field of ligand design, as well as those who work in the many areas in which the impact of ancillary ligand design has proven significant, for example synthetic organic chemistry, catalysis, medicinal chemistry, polymer science and materials chemistry.
Download or read book Metal Mediated Template Synthesis of Ligands written by Otilia Costisor and published by World Scientific. This book was released on 2004 with total page 316 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book surveys the relatively new area of the synthesis of organic ligands when metal ions act as a template. In the last fifty years this field has undergone an explosive development, marked by a great amount of literature. The material in the book has been arranged according to the type of chemical reaction involved. In this frame, the basic principles of metal template reactions and the shape of the molecules are considered. Designed to satisfy the demands of students, young researchers doing their PhDs, and those working in the field of coordination chemistry, the book details the role of the metal ions and the specific properties of the formed complexes. Metal Mediated Template Synthesis of Ligands offers a comprehensive analysis with wide-ranging references and provides an extensive overview of research on metal-directed organic ligands over the past five decades. Contents: The Template Effect; Alkylation Reactions; Schiff Condensation; Mannich Condensation; Self Condensation of Nitriles; Self-Assembled Systems. Readership: Upper level undergraduates, graduate students, academics, researchers industrialists in inorganic, solid-state, supramolecular and organic chemistry.
Download or read book Luminescent and Photoactive Transition Metal Complexes as Biomolecular Probes and Cellular Reagents written by Kenneth Kam-Wing Lo and published by Springer. This book was released on 2015-06-30 with total page 266 pages. Available in PDF, EPUB and Kindle. Book excerpt: The series Structure and Bonding publishes critical reviews on topics of research concerned with chemical structure and bonding. The scope of the series spans the entire Periodic Table and addresses structure and bonding issues associated with all of the elements. It also focuses attention on new and developing areas of modern structural and theoretical chemistry such as nanostructures, molecular electronics, designed molecular solids, surfaces, metal clusters and supramolecular structures. Physical and spectroscopic techniques used to determine, examine and model structures fall within the purview of Structure and Bonding to the extent that the focus is on the scientific results obtained and not on specialist information concerning the techniques themselves. Issues associated with the development of bonding models and generalizations that illuminate the reactivity pathways and rates of chemical processes are also relevant. The individual volumes in the series are thematic. The goal of each volume is to give the reader, whether at a university or in industry, a comprehensive overview of an area where new insights are emerging that are of interest to a larger scientific audience. Thus each review within the volume critically surveys one aspect of that topic and places it within the context of the volume as a whole. The most significant developments of the last 5 to 10 years should be presented using selected examples to illustrate the principles discussed. A description of the physical basis of the experimental techniques that have been used to provide the primary data may also be appropriate, if it has not been covered in detail elsewhere. The coverage need not be exhaustive in data, but should rather be conceptual, concentrating on the new principles being developed that will allow the reader, who is not a specialist in the area covered, to understand the data presented. Discussion of possible future research directions in the area is welcomed. Review articles for the individual volumes are invited by the volume editors. Readership: research scientists at universities or in industry, graduate students Special offer For all customers who have a standing order to the print version of Structure and Bonding, we offer free access to the electronic volumes of the Series published in the current year via SpringerLink.
Download or read book Ligands written by Paula Gawryszewska and published by Nova Science Publishers. This book was released on 2014 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: To meet the search for new therapeutic compounds this book summarises the research on biologically active organic molecules (chapters 1, 2 and 3), metal complexes with biological activity (chapter 4), and shows the possibilities for co-ordination chemistry in the planning of metal complexes with interesting properties for application (chapters 5, 6, 7, 8, and 9). It should be remembered that in the design of a new potentially active metallodrug, beyond the nature of the metal, the choice of appropriate ligands which affect the thermodynamic and kinetic stability, as well as the solubility and lipophilicity of the complexes is of paramount importance. The information contained in the book concerns: 1) the interactions involving the members of the Nuclear Receptor superfamily and their ligands; 2) the role of chemokine ligands and their receptors in normal and disease processes, and the emerging therapeutic approaches of using chemokine antagonists for appropriately targeted therapy; 3) the inhibition of alkaline phosphatases by calix[4]arenes functionalysed at the macrocyclic upper rim by one or two methylenebisphosphonic acid fragments; 4) the main biological applications, enzyme modelling and antiproliferative and antimicrobial activity of such scorpionate-type complexes, which are classified by ligand and also by transition metal; 5) the silver(I) discrete and polymeric coordination compounds bearing 1,3,5-triaza-7-phosphaadamantane or its derivatives towards engineering functional silver-organic frameworks (MOFs); 6) arylhydrazones of methylene active nitriles and their use as starting materials for the generation of new organic and coordination compounds; 7) amidophosphate ligands as promising sensitisers of lanthanide ions emission; 8) N-acetylsalicylhydrazidate as a versatile ligand for the synthesis of higher nuclearity metal complexes, which are illustrated herein along with their applications; 9) the chemistry and some applications of formazans which can be used for the simultaneous selective determination of several metal cations. All chapters were compiled by renowned scientists, providing both beginners in the field and advanced researchers with comprehensive information on the subject.
Download or read book The Design and Synthesis of Luminescent Iridium and Platinum Complexes Featuring Bi Tri and Tetra dentate Ligands written by David Patrick O'Farrell and published by . This book was released on 2020 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Design Synthesis and Functionalization of Luminescent Alkynylgold i Complexes with Pi Conjugated Ligands written by YAU-HIN. HONG and published by . This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
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 Host Guest Chemistry of Rhodamine Derivatives and Their Transition Metal Complexes written by Ho-Chuen Lam 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, "Design, Synthesis and Host-guest Chemistry of Rhodamine Derivatives and Their Transition Metal Complexes" by Ho-chuen, Lam, 林浩銓, 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: New classes of luminescent transition metal complexes, including the systems of rhenium(I) tricarbonyl diimine, cyclometalated iridium(III) diimine, cyclometalated rhodium(III) diimine, ruthenium(II) diimine and ruthenium(II) terpyridine complexes tethered with rhodamine moieties, have been synthesized. The X-ray crystal structure of one of the cyclometalated rhodium(III) diimine complexes with rhodamine pendants, [Rh(SPLC2N2)(ppy)2](PF6) has been determined. The molecular structure of [Rh(SPLC2N2)(ppy)2](PF6) showed a distorted octahedral geometry and the rhodamine moiety was found in a spirolactam closed-ring form. All of them were found to exhibit emission in fluid solution. The emissions of rhenium(I) tricarbonyl diimine and ruthenium(II) polypyridyl complexes are derived from the triplet metal-to-ligand charge transfer (3MLCT) excited state, i.e. from dπ orbital of the rhenium(I) or ruthenium(II) metal center to the π* orbital of the diimine ligand; while that of cyclometalated iridium(III) diimine complexes is (3MLCT) [dπ(Ir) → π*(N DEGREESN)] and that of cyclometalated rhodium(III) diimine complexes involves the (3IL) [π → π*(N DEGREESC)] excited state, probably mixed with (3MLCT) [dπ(Rh) → π*(N DEGREESC)] character. The cation-binding properties of these complexes toward alkali, alkaline-earth and transition-metal cations were investigated by electronic absorption and emission spectrophotometries. Some of them were found to exhibit new low-energy absorption and emission bands, characteristic of the rhodamine absorption and emission, with high selectivity and sensitivity for certain transition metal cations. A series of rhodamine-appended Schiff base organic compounds has also been synthesized in order to explore their capability as luminescent lanthanide ion sensors. The lanthanide ion binding properties of one of the compounds in acetonitrile were examined. Upon addition of lanthanide ions, new intense low-energy electronic absorption and emission bands were also observed, characteristic of the rhodamine absorption and emission, demonstrating its lanthanide ion sensing behaviour. DOI: 10.5353/th_b5060562 Subjects: Rhodium compounds - Synthesis Transition metal complexes - Synthesis
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.
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
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 Yu-Lut Leung and published by . This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Ligand Design and Synthesis for the Emission of Circularly Polarized Luminescence From Copper I and Uranium VI written by Erin Braker and published by . This book was released on 2021 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
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
