Download or read book Synthesis Characterization and Photophysical Properties of Chalcogenido Phosphinidene and Alkynyl Complexes of Gold I and Its Congener and Their Supramolecular Assembly Arising from Metal Metal Interactions written by Kwok-Ming Lee 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, "Synthesis, Characterization and Photophysical Properties of Chalcogenido, Phosphinidene and Alkynyl Complexes of Gold (I) and Its Congener and Their Supramolecular Assembly Arising From Metal--metal Interactions" by Kwok-ming, Lee, 李國明, 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_b4598342 Subjects: Gold compounds - Synthesis Complex compounds - Synthesis Photochemistry Supramolecular chemistry
Download or read book Synthesis Characterization and Photophysical Properties of Chalcogenido Phosphinidene and Alkynyl Complexes of Gold I and Its Congener and Their Supramolecular Assembly Arising from Metal metal Interactions written by Kwok-ming Lee and published by . This book was released on 2011 with total page 692 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Download or read book Design Synthesis Characterization and Luminescence Properties of Alkynylgold i Complexes written by Sung-Kong Yip 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, Characterization and Luminescence Properties of Alkynylgold(I) Complexes: Strategies Towards Supramolecular Architectures and Host Guest Chemistry" by Sung-kong, Yip, 葉崇江, 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, CHARACTERIZATION AND LUMINESCENCE PROPERTIES OF ALKYNYLGOLD(I) COMPLEXES STRATEGIES TOWARDS SUPRAMOLECULAR ARCHITECTURES AND HOST GUEST CHEMISTRY Submitted by YIP Sung Kong for the degree of Doctor of Philosophy at The University of Hong Kong in July 2005 A series of luminescent dialkynylaurate(I) complexes, [X][Au(C CR) ] [X = Bu N, R = C H OMe-p, C H OHex-p, C H Oct-p, C H Cl-p, C H CF -p, 1-naphthyl 4 6 4 6 4 6 4 6 4 6 4 3 (Np), 9-anthracenyl (An), 1-pyrenyl (Pyr); X = PPN, R = Pyr] have been synthesized. The X-ray crystal structures of [BuN][Au(CCCHOMe-p)] and 4 64 2 [BuN][Au(CCCHCF-p)] showed the presence of intermolecular hydrogen 4 64 3 2 bonds with bonding distances of ca. 2.599 - 2.620 A. The related pentanuclear gold(I)-copper(I) and -silver(I) mixed-metal alkynyl complexes, [BuN][AuM(CCCH-R-p) ] [M = Cu, R = OMe, OBu, OHex, Et; M = Ag, R = Et, 4 32 64 6 OHex] have been synthesized. The emission origin was tentatively assigned as derived from triplet states of metalloligand-to-metal cluster core charge transfer [Au(C CR) M Au ] (M = Cu, Ag) origin, probably mixed with some metal- 2 2 3 perturbed intraligand *(C C) character. Through the utilization of alkynylcalix[4]crown as ligands, dinuclear gold(I) 1 2 3 alkynylcalix[4]crown-5 complexes, [(R P)Au] L [R = Tol-o, L = L; R = Ph, L = L, L ], 3 2 4 5 6 1 tetranuclear gold(I) alkynylcalix[4]crown assemblies, [Au (L') ] [L' = L, L, L, L ] and 4 2 a mixed-metal gold(I)-copper(I) alkynylcalix[4]crown complex, [Au Cu (L ) ] have 2 2 2 been synthesized. The X-ray crystal structures of all the dinuclear gold(I) complexes, 4 1 4 [Au (L') ] [L' = L, L ] and [Au Cu (L ) ] have been determined. The X-ray crystal 4 2 2 2 2 structures of [Au(L')] showed that two of the gold(I) centers were each 4 2 -coordinated to two alkynyl units, while the other two were each -coordinated by 2 2 the two alkynyl units in an unusual planar, -coordination mode, which was the first of its kind for gold(I) complexes. The Au Au distances between adjacent gold atoms were in the range of 3.1164(11) 3.2118(10) A, indicative of the presence of significant Au Au interactions. The emissive origin of [Au (L') ] was assigned as 4 2 derived from a triplet state of a metal cluster-centered ds/dp character, probably with some mixing of a metal-perturbed intraligand character, while the emission of [Au Cu (L ) ] was assigned to have similar character, but with modification by 2 2 2 Au Cu interactions. The binding properties of the dinuclear gold(I) complexes toward alkali metal ions have been studied. Dinuclear gold(I) complexes, [{Ph PN(R)PPh }Au (C CR') ] [R = Pr, R' = Ph, 2 2 2 2 C H OMe-p, C H Me-p, C H Cl-p; R = C H OMe-p, R' = Ph], have been synthesized 6 4 6 4 6 4 6 4 by deploymerization of alkynylgold polymers using bis(diphenylphosphino)amines as ligands. The X-ray crystal structures of [{PhPN(Pr)PPh}Au(C CPh)] and 2 2 2 2 [{PhPN(Pr)PPh}Au(C CCHOMe-p)]] revealed the presence of short 2 2 2 6 4 2 intramolecular Au Au contacts with the Au Au distances of 2.8404(8) and 3.0708(7) A, respectively. The photophysical properties of the complexes have been studied and their emission orig
Download or read book Modern Supramolecular Gold Chemistry written by Antonio Laguna and published by John Wiley & Sons. This book was released on 2008-09-26 with total page 525 pages. Available in PDF, EPUB and Kindle. Book excerpt: Filling a gap in our systematic knowledge of gold, this monograph covers the fundamental aspects, while also considering new applications of gold compounds in catalysis, as nanoparticles, and their potential application as luminescent compounds. Written by an eminent team of authors from academia, the book analyzes the current status of gold chemistry, its special characteristics, oxidation states and main type of complexes, before going on to look at the synthesis of supramolecular aggregates due to the formation of gold-gold, gold-metal interactions or other secondary bonds. Final sections deal with LEDs, solvoluminescent and electroluminescent materials, liquid crystals and catalysis. While of interest to advanced chemistry students, this book is also useful for researchers interested in the chemistry of gold and its applications, as well as those involved in metal-metal interactions, heteronuclear chemistry or in the optical properties of coordination compounds.
Download or read book Design Synthesis and Functionalization of Stimuli responsive Luminescent Gold i Alkynyl Chalcogenido and Phosphinidene Complexes written by 朱劼怡 and published by . This book was released on 2019 with total page 367 pages. Available in PDF, EPUB and Kindle. Book excerpt:
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 Novel Luminescent Cyclometalated Gold III Alkynyls written by Ling-Ling 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, "Novel Luminescent Cyclometalated Gold (III) Alkynyls: Design, Synthesis, Photophysics and Their Multinuclear Assemblies" by Ling-ling, Hung, 熊靈玲, 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 NOVEL LUMINESCENT CYCLOMETALATED GOLD(III) ALKYNYLS - DESIGN, SYNTHESIS, PHOTOPHYSICS AND THEIR MULTINUCLEAR ASSEMBLIES Submitted by HUNG Ling Ling for the Degree of Doctor of Philosophy at The University of Hong Kong in November 2007 A new class of luminescent mononuclear cyclometalated gold(III) complexes containing various monoynyl ligands, [Au(RC DEGREESN(R′) DEGREESCR)(C≡CR′′)], i.e. [Au(C DEGREESN DEGREESC)(C≡CR′′)] (HC DEGREESN DEGREESCH = 2,6-diphenylpyridine; R′′ = C H, C H-Cl-p, 6 5 6 4 C H-C H -p, C H-OCH -p, C H-NO -p, C H-NH -p, C H-N(CH ) -p, 6 4 6 13 6 4 3 6 4 2 6 4 2 6 4 3 2 t t t t C H-N(C H ) -p, C H ), [Au( BuC DEGREESN DEGREESC Bu)(C≡CR′′)] (H BuC DEGREESN DEGREESCBuH = 2,6- 6 4 6 5 2 6 13 bis(4-tert-butylphenyl)pyridine; R′′ = C H, C H-NH -p, Si(CH ), H), 6 5 6 4 2 3 3 [Au(FC DEGREESN DEGREESCF)(C≡CR′′)] (HFC DEGREESN DEGREESCFH = 2,6-bis(4-fluorophenyl)pyridine; R′′ = C H, 6 5 C H-NH -p) and [Au(C DEGREESNTol DEGREESC)(C≡CC H-C H -p)] (HC DEGREESNTol DEGREESCH = 2,6- 6 4 2 6 4 6 13 diphenyl-4-p-tolylpyridine) have been synthesized. Most of the complexes have been structurally determined by X-ray crystallography which revealed the presence of intermolecular π-π stacking interaction with interplanar separations between [Au(RC DEGREESN(R′) DEGREESCR)] units of ca. 3.343-3.570 A. The lowest-lying excited states of 3 these complexes in dichloromethane were assigned as the metal-perturbed IL [π → π*(RC DEGREESN(R′) DEGREESCR)] origin, with substantial charge transfer character from the aryl ring to the pyridyl unit, whereas a switch in the lowest-lying excited states origin to LLCT [π(C≡CC H NR′′′ ) → π*(RC DEGREESN(R′) DEGREESCR)] was observed in complexes 6 4 2 containing aminophenyl alkynyl ligands. The low-energy emissions in the solid state were attributed to the π-π excimeric intraligand phosphorescence, arising from the intermolecular π-π stacking interactions of the RC DEGREESN(R′) DEGREESCR ligands in the solid state as revealed from the crystal packing diagrams. A series of luminescent mononuclear cyclometalated gold(III) complexes with various oligoynyl ligands, [Au(RC DEGREESN DEGREESCR)(C≡CR′)] (R = H, R′ = C≡CH, C H-C≡CH, C≡CC H, C≡CC H-CH -p, C≡CC H-CF -p, C≡CC H-NH -p, 6 4 6 5 6 4 3 6 4 3 6 4 2 C≡C-C≡CC H; R = Bu, R′ = C≡CH, C H-C≡CH) have also been synthesized. 6 5 6 4 The di- and trinuclear cyclometalated gold(III) alkynyl complexes, [1,4- t t t t {Au( BuC DEGREESN DEGREESC Bu)C≡C} C H ] and [1,3,5-{Au( BuC DEGREESN DEGREESC Bu)C≡C} C H ], have also 2 6 4 3 6 3 been prepared. The X-ray crystal structures of [Au(RC DEGREESN DEGREESCR)(C≡CR′)] (R = H, R′ = C≡CH, C H-C≡CH, C≡CC H-CH -p, C≡CC H-CF -p; R = Bu, R′ = 6 4 6 4 3 6 4 3 t t C H-C≡CH) and [1,3,5-{Au( BuC DEGREESN DEGREESC Bu)C≡C} C H ] have been determined. The 6 4 3 6 3 t t molecular structure of [1,3,5-{Au( BuC DEGREESN DEGREESC Bu)C≡C} C H ] showed the twisting of 3 6 3 t t the three coordination planes, [Au( BuC DEGREESN DEGREESCBu)], relative to the central phenyl ring with dihedral angles of 6.1, 48.4 and 60.7. Similarly, the emissions of most of the complexes in fluid solution were attributed to the metal-perturbed IL [π → π*(RC DEGREESN DEGREESCR)] phosphorescence with substantial charge transfer character from the aryl group to the pyridyl unit, while the emission origin was assigned as derived 3 f
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 &
