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Design Synthesis And Characterization Of Luminescent Dinuclear And Polynuclear Complexes Of Goldi And Platinumii With Alkynylcalix4arene And Bridging Sulfido Ligands
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Book Synopsis Design, Synthesis and Characterization of Luminescent Dinuclear and Polynuclear Complexes of Gold(I) and Platinum(II) with Alkynylcalix[4]arene and Bridging Sulfido Ligands by : 侯嘉華
Download or read book Design, Synthesis and Characterization of Luminescent Dinuclear and Polynuclear Complexes of Gold(I) and Platinum(II) with Alkynylcalix[4]arene and Bridging Sulfido Ligands written by 侯嘉華 and published by . This book was released on 2014 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Design, Synthesis and Photophysical Properties of Dinuclear Platinum (II) Complexes with Varying Bridging and Cyclometalating Ligands by : Subhangi Roy
Download or read book Design, Synthesis and Photophysical Properties of Dinuclear Platinum (II) Complexes with Varying Bridging and Cyclometalating Ligands written by Subhangi Roy and published by . This book was released on 2018 with total page 189 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis DESIGN & SYNTHESIS OF LUMINESC by : Suk-Hang Lam
Download or read book DESIGN & SYNTHESIS OF LUMINESC written by Suk-Hang Lam and published by Open Dissertation Press. This book was released on 2017-01-26 with total page 292 pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design and Synthesis of Luminescent Platinum(II) and Gold(III) Complexes With Tridentate Pincer-type Ligands: From Computational Study to Experiments and Application Studies" by Suk-hang, Lam, 林淑恒, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN AND SYNTHESIS OF LUMINESCENT PLATINUM(II) AND GOLD(III) COMPLEXES WITH TRIDENTATE PINCER-TYPE LIGANDS - FROM COMPUTATIONAL STUDY TO EXPERIMENTS AND APPLICATION STUDIES Submitted by LAM Suk Hang for the degree of Doctor of Philosophy at The University of Hong Kong in June 2015 Square planar platinum(II) and gold(III) complexes possess unique spectroscopic and photophysical properties which enable them as promising candidates for many applications such as optoelectronic devices and biological sensors. The understanding of the intrinsic properties of these complexes is therefore essential to optimize their performance as well as provide guidance on the molecular design for specific applications. This thesis aims to provide useful insights for the molecular design strategies with the aid of computational studies to tune the electronic properties of these complexes and electroluminescence studies in the fabrication of organic light-emitting devices (OLEDs). Computational studies have been performed to inspect electronic structures and photophysical properties as well as their correlation with the nature of ancillary ligands in the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene, [Pt(bzimb)(C≡C-R)], 1,3-bis-hetero-azolylbenzenes, [Pt(N DEGREESC DEGREESN)(C≡C-R)], and pyridine-based N-heterocyclic carbene, [Pt(NHC)(C≡C-R)] . It was found that the emission of the arylalkynylplatinum(II) complexes with pyridine-based N-heterocyclic carbene ligand was originated from the triplet alkynyl-to-tridentate pincer ligand-to-ligand charge transfer excited state mixed with platinum-to-tridentate pincer metal-to-ligand charge transfer character, and the excited state energy was found to be red-shifted according to the increasing π electron-donating ability of the aryl group attached to the alkynyl ligand. On the other hand, the emission energies of the platinum(II) complexes of 1,3-bis(N-alkylbenzimidazol-2′-yl)benzene and 1,3-bis-hetero-azolylbenzenes were found to be dependent on the different electron-donating substituents on the pincer ligands. Calculations have also been performed on the representative alkynylplatinum(II) + + complexes [Pt(trpy)(C≡C-R)] (trpy = 2,2′ 6′,2′′-terpyridine), [Pt(bzimpy)(C≡C-R)] (bzimpy = 2,6-bis(N-alkylbenzimidazol-2′-yl)pyridine) and [Pt(bzimb)(C≡C-R)] as well as alkynylgold(III) complexes [Au(C DEGREESN DEGREESC)(C≡C-R)] (C DEGREESN DEGREESC = 2,6-diphenylpyridine), [Au{C(Np) DEGREESN DEGREESC(Np)}(C≡C-R)] (C(Np) DEGREESN DEGREESC(Np) = 2,6-di(2-naphthyl)pyridine) and [Au(N DEGREESN DEGREESN)(C≡C-R)] (N DEGREESN DEGREESN = 2,6-bis(1H-benzimidazol-2-yl)pyridine) in order to have a better understanding on their nature of the emissive origins as well as the radiative and nonradiative processes. In particular, factors governing the ordering of the triplet excited states and radiative decay rate constants of the emissive state ( ES) have been examined. Their potential energy profiles for the deactivation process from the ES via triplet metal-centered states have also been explored. This study revealed for the first time the potential energy profiles for the thermal deactivation pathway of square planar platinum(II) and gold(III) complexes. In addition to the computational
Book Synopsis Design and Synthesis of Luminescent Mono- And Dinuclear Platinum(ii) Alkynyl Terpyridine Complexes by : Hoi-Yiu Chan
Download or read book Design and Synthesis of Luminescent Mono- And Dinuclear Platinum(ii) Alkynyl Terpyridine Complexes written by Hoi-Yiu Chan 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 Mono- and Dinuclear Platinum(II) Alkynyl Terpyridine Complexes: From Photophysics to Aggregation and Self-assembly" by Hoi-yiu, Chan, 陳凱耀, 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 MONO- AND DINUCLEAR PLATINUM(II) ALKYNYL TERPYRIDINE COMPLEXES - FROM PHOTOPHYSICS TO AGGREGATION AND SELF-ASSEMBLY submitted by CHAN Hoi Yiu for the degree of Doctor of Philosophy at The University of Hong Kong in August 2006 A series of mononuclear alkynylplatinum(II) terpyridyl complexes, [Pt(trpy)({C{ C} C H )]PF, [Pt(trpy)({C{ C} C H CF -4)]PF, n 6 5 6 n 6 4 3 6 [Pt(trpy)({C{ C} C H CH -4)]PF, and [Pt( Bu trpy)(C{ C C{ C C H )]PF (n = n 6 4 3 6 3 6 5 6 2, 3), have been synthesized. The X-ray crystal structures of the two forms of [Pt(trpy)(C{ C C{ C C H )]PF, [Pt(trpy)(C{ C C{ C C{ C C H CH -4)]PF and 6 5 6 6 4 3 6 [Pt( Bu trpy)(C{ C C{ C C H )]PF have been determined. Dinuclear and 3 6 5 6 trinuclear alkynylplatinum(II) terpyridyl complexes, [1,4- {Pt(trpy)C{ C} C H ](OTf), [1,4-{Pt( Bu trpy)C{ C} C H ](OTf), [2,5- 2 6 4 2 3 2 6 4 2 {Pt(trpy)C{ C} C H S](OTf), [2,5-{Pt( Bu trpy)C{ C} C H S](OTf) and [1,3,5- 2 4 2 2 3 2 4 2 2 {Pt( Bu trpy)C{ C} C H ](OTf) have been successfully synthesized. The X-ray 3 3 6 3 3t crystal structure of [1,4-{Pt( Bu trpy)C{ C} C H ](OTf) has also been 3 2 6 4 2 determined. The luminescence properties of these complexes have been studied and their lowest-lying excited states in fluid solution and in the glass state were tentatively assigned as admixture of MLCT [dS (Pt)ĺ S *(trpy)] and LLCT [S (C{ C)ĺ S *(trpy)] origin, whereas the low-energy emissions in the solid state were attributed to triplet metal metal-to-ligand charge transfer ( MMLCT) phosphorescence, resulting from significant Pt---Pt interactions in the solid state. Besides, a series of luminescent platinum(II) terpyridyl alkynyl complexes with different counter anions, [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF, ClO, 6 4 BF, BPh ), [Pt(trpy)(C{ C C H )]X (X = OTf, PF, ClO, BF ) and 4 4 6 5 6 4 4 complexes with various substituents on the alkynyl and terpyridyl ligands, [Pt(trpy)(C{ CC H OCH-4)]OTf, [Pt(4'-CH O trpy)(C{ C C H )]OTf, 6 4 3 3 6 5 [Pt( Bu trpy)(C{ C C{ CH)]OTf, [Pt(trpy)(C{ CC H {CH NMe }-4)](OTf), 3 6 4 2 3 2 [Pt(trpy)(C{ C C{ C CH NMe )](OTf) and [Pt(trpy)(C{ C C{ C CH OH)]OTf 2 3 2 2 have been synthesized and their photophysical properties have been stuided. The X-ray crystal structure of [Pt(trpy)(C{ C C H )]ClO and 6 5 4 [Pt( Bu trpy)(C{ C C{ C H)]OTf have been determined. The solid-state absorption and emission spectra showed low-energy bands, which were assigned as derived from MMLCT origin. Solvent-induced aggregation studies of these complexes in solution showed that the color of the aggregates could be very different for different counter-ions, indicating that counter-ions played an important role in governing the degree of aggregation and the extent of interactions within these aggregates. Addition of various anions to solutions of [Pt(trpy)(C{ C C{ C H)]X (X = OTf, PF ) produced anion-induced color 6changes upon solvent-induced aggregation, showing that these complexes might serve as potential colorimetric anion probes. The effect of temperature on the aggregation properties of the complexes has also been explored. New low-energy absorption and emission bands were found upon a reduction of temperature, attributable to the formation o
Book Synopsis Design, Synthesis, Characterization and Luminescence Properties of Alkynylgold(i) Complexes by : Sung-Kong Yip
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
Book Synopsis Synthesis and Characterization of Luminescent Gold(III) Complexes by : Amanda N. Sulicz
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 Synopsis Design and Synthesis of Luminescent Mono- and Dinuclear Platinum(II) Alkynyl Terpyridine Complexes by : Hoi-yiu Chan
Download or read book Design and Synthesis of Luminescent Mono- and Dinuclear Platinum(II) Alkynyl Terpyridine Complexes written by Hoi-yiu Chan and published by . This book was released on 2006 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Cyclometalated Gold (III) Complexes with Ancillary N-Heterocyclic Carbene and Alkynyl Ligands by : Ka-Man Au
Download or read book Luminescent Cyclometalated Gold (III) Complexes with Ancillary N-Heterocyclic Carbene and Alkynyl Ligands written by Ka-Man Au and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Luminescent Cyclometalated Gold (III) Complexes With Ancillary N-heterocyclic Carbene and Alkynyl Ligands: From Design, Synthesis, Photophysics to Supramolecular Assembly and Functions" by Ka-man, Au, 區嘉雯, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: A library of luminescent cyclometalated gold(III) complexes containing various bis-cyclometalating R-C DEGREESN DEGREESC ligands derived from 2,6-diphenylpyridine and ancillary alkynyl ligands, [Au(R-C DEGREESN DEGREESC)(C≡CR')], has been synthesized. Some of the complexes have been structurally determined by X-ray crystallography. These complexes were found to exhibit intense emission in dichloromethane solution at 298 K, originating from metal-perturbed triplet intraligand (IL) excited states of the R-C DEGREESN DEGREESC ligand, with substantial charge transfer character from the aryl moiety to the pyridyl ring. In the presence of electron-rich alkynyl ligands, the emission origin could be switched to an alkynyl-to-cyclometalating ligand ligand-to-ligand charge transfer (LLCT) excited state. This class of complexes was also demonstrated to show rich electroluminescence properties as emitters in organic light-emitting devices. In addition, the supramolecular assembly of this class of complexes has also been revealed in gelation studies. N-Heterocyclic carbenes have been incorporated into the gold(III) metal center to prepare a series of luminescent mononuclear and dinuclear gold(III) complexes, [{Au(C DEGREESN DEGREESC)}n(NHC)](PF6)n and [{Au(tBuC DEGREESN DEGREESCtBu)}n(NHC)]- (PF6)n (n = 1, 2). The X-ray crystal structures of most of the complexes have been determined. The emissions of these complexes were assigned to originate from the metal-perturbed intraligand excited state of the bis-cyclometalating ligand. One of the C2-bridged dinuclear complexes was found to exhibit two distinct reduction couples, tentatively correlated to the presence of significant intramolecular π-π interaction in the complex. Two novel series of luminescent mononuclear alkynylgold(III) complexes, [Au(C DEGREESN)(C≡CR)2] (HC DEGREESN = 2-phenylpyridine (Hppy) and derivatives) and [Au(C DEGREESN DEGREESN)(C≡CR)]PF6 (HC DEGREESN DEGREESN = 6-phenyl-2,2'-bipyridine and derivatives), have been synthesized. Some of the X-ray crystal structures have been determined. The former class of complexes with bidentate C DEGREESN ligands has been observed to show tunable emission spanning across the visible spectrum from 462 to 697 nm. With the exception of [Au(ppy)(C≡C-C6H4-NH2-p)2] which showed a low-energy band originated from a 3LLCT [π(C≡C-C6H4-NH2)→π*(C DEGREESN)] excited state, all complexes exhibited vibronic-structured emission bands originated from the intraligand transition of the cyclometalating C DEGREESN ligand in dichloromethane solution at 298 K. On the other hand, most of the complexes with the tridentate C DEGREESN DEGREESN-type ligand have been observed to exhibit vibronic-structured emission bands attributed to the intraligand transition of the C DEGREESN DEGREESN ligand in low-temperature butyronitrile glass. DOI: 10.5353/th_b4775268 Subjects: Organogold compounds - Synthesis Carbenes (Methylene compounds) Heterocyclic compo
Book Synopsis Design and Synthesis of Luminescent Platinum(II) and Gold(III) Complexes with Tridentate Pincer-type Ligands by : 林淑恒
Download or read book Design and Synthesis of Luminescent Platinum(II) and Gold(III) Complexes with Tridentate Pincer-type Ligands written by 林淑恒 and published by . This book was released on 2015 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis and Characterization of Dinuclear Gold(I) Complexes Containing Dithiolates and Phosphines Or Bis(Diphosphine) Donor Ligands by : Rosa Maria Davila
Download or read book Synthesis and Characterization of Dinuclear Gold(I) Complexes Containing Dithiolates and Phosphines Or Bis(Diphosphine) Donor Ligands written by Rosa Maria Davila and published by . This book was released on 1993 with total page 226 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis 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
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
Book Synopsis DESIGN, SYNTHESIS, PHOTOPHYSICAL, AND ELECTROCHEMICAL STUDIES OF NOVEL CYCLOMETALATED PYRAZOLATE-BRIDGED DINUCLEAR PLATINUM(II) COMPLEXES by : Arnab Chakraborty
Download or read book DESIGN, SYNTHESIS, PHOTOPHYSICAL, AND ELECTROCHEMICAL STUDIES OF NOVEL CYCLOMETALATED PYRAZOLATE-BRIDGED DINUCLEAR PLATINUM(II) COMPLEXES written by Arnab Chakraborty and published by . This book was released on 2014 with total page 154 pages. Available in PDF, EPUB and Kindle. Book excerpt: The present dissertation describes the synthesis, photophysical, and electrochemical properties of a library of pyrazolate-bridged dinuclear cyclometalated platinum(II) complexes. All the complexes investigated here were synthesized with complete characterization. Both the steady state, as well as the time-resolved photophysical techniques employed during the study, helped in defining the photophysical behavior exhibited by such complexes. All the dinuclear Pt(II) complexes discussed here can be expressed by a general formula [Pt(C^N)(µ-R2pz)]2; where C^N is a cyclometalating ligand, and R2Pz are various 3,5-disubstituted pyrazolates. The bridging pyrazolates initiates the metal-metal interaction by building up steric strain within the resulting A-frame topology of the complexes. All the Pt(II) complexes are strongly emissive at room temperature. The influence of the nature of cyclometalating ligand, and the bridging pyrazolates on the photophysical and electrochemical behavior displayed by the complexes were thoroughly investigated. Both room temperature and low temperature measurements aided in distinguishing the nature of lowest energy emissive state present in such complexes. The second part of this dissertation merges our research interest in metal-organic light harvesting chromophores and MLCT complexes with extended lifetime. The dinuclear platinum(II) complexes investigated, have a 4-piperidinyl-1,8-naphthalimide (PNI) unit covalently attached to the cyclometalating 2-phenylpyridine ligand. The resulting bichromophoric complex displayed an enhanced light harvesting ability as compared to the parent dimers. Our study is an effort towards understanding the influence of increased metal-metal interaction on the establishment of a thermal equilibrium between the 3PNI and the 3MMLCT excited states.
Book Synopsis Syntheses, Characterization and Photophysical Properties of Platinum(ii) and Gold(i) Complexes Containing Ortho- And Meta-Oligo(phenyleneethynylene) Ligands by : 朱明新
Download or read book Syntheses, Characterization and Photophysical Properties of Platinum(ii) and Gold(i) Complexes Containing Ortho- And Meta-Oligo(phenyleneethynylene) Ligands written by 朱明新 and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Syntheses, Characterization and Photophysical Properties of Platinum(II) and Gold(I) Complexes Containing Ortho- and Meta-oligo(phenyleneethynylene) Ligands" by 朱明新, Mingxin, Zhu, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled SYNTHESES, CHARACTERIZATION AND PHOTOPHYSICAL PROPERTIES OF PLATINUM(II) AND GOLD(I) COMPLEXES CONTAINING ORTHO- AND META- OLIGO(PHENYLENEETHYNYLENE) LIGANDS Submitted by Zhu Mingxin for the degree of Doctor of Philosophy at The University of Hong Kong in March 2008 Metal complexes containing oligo(phenyleneethynylene) (PE) are of great importance in photophysics and material science. The syntheses, characterizations and photophysical properties of the light-emitting platinum(II) and gold(I) complexes with flexible ortho- and meta-PE and 2,5-diphenyl-1,3,4-oxadiazole ligands were described. Several novel dinuclear terpyridyl platinum(II) complexes with ortho-PE ligands were synthesized and their crystal structures were determined. The t t 2+ t platinum(II) complexes [( Bu tpy)Pt-(ortho-PE)-Pt( Bu tpy)] ( Bu tpy = 4,4′,4″-tri- 3 3 3 tert-butyl-2,2′ 6′,2″-terpyridine) adopted a helical conformation in their crystal structures, and their phosphorescence recorded in acetonitrile/water mixtures shifted to lower energy with enhanced intensity when the water content increased. A hydrophobic folding process was suggested for the complexes with long ortho-PE(n) (n >= 3), and the red-shifted and enhanced phosphorescence was attributed to inter- and intra-molecular π-π interactions. The mononuclear terpyridine and C DEGREESN DEGREESN capped t + platinum(II) complexes [( Bu tpy)Pt-(ortho-PE)] and [(C DEGREESN DEGREESN)Pt-(ortho-PE)] (HC DEGREESN DEGREESN = 6-phenyl-2,2′-bipyridine) were studied for comparison. A series of mononuclear and dinuclear ortho- and meta-PE gold(I) complexes, [(PCy )Au-(ortho-PE)] (PCy = tricyclohexylphosphine), [(PCy )Au-(ortho-PE)- 3 3 3 Au(PCy)], [(PCy )Au-(meta-PE)] and [(PCy )Au-(meta-PE)-Au(PCy)] were 3 3 3 3 synthesized to examine the effect of ortho- and meta-conjugation. A ππ* emission of the PE ligands was switched on at room temperature by the attachment of [Au(PCy )] fragment due to the heavy atom effect. The delayed fluorescence from the ππ* excited states of the PE ligands was observed, and a triplet-triplet annihilation pathway was proposed. The difference in conjugation of para-, ortho- and meta-PE ligation was examined by comparison of the singlet and triplet emission energies of the gold(I) complexes. By extrapolating the plot of the emission energy against the PE chain length in the complex, the triplet emission energies of poly(ortho-PE) and poly(meta-PE) were estimated to be 530 and 470 nm respectively. These complexes together with the reported [Au(PCy )] complexes containing para-PE ligands, constitute a complete class of [Au(PCy )] supported phenyleneethynylene complexes. 2+ New ortho-PE ligands were used as flexible linkers for [Pt(PEt ) ] moieties 3 2 (PEt = triethylphosphine). Three neutral platinum(II) macrocycles with the maximum ring size of 60 atoms were synthesized and their crystal structures were determined, 31 revealing decreased nuclearity when the ortho-PE length increases. The P NMR spectra of [Pt(PEt ) {ortho-PE(5)}] with a rigid conformation at various temperatures 3 2 are consistent with the calculated spectrum of ABX spin system. A series of platinum(II)-bis(triethylphosphine) complexes containing 2,5- diphenyl-1,3,4-oxadiazole moiety were synthesized, and
Book Synopsis Synthesis, Luminescence and Host-Guest Chemistry of Mono- and Dinuclear Platinum(ii) Complexes of Pyridyl and Diphosphine Ligands by : Pui-Ling Tang
Download or read book Synthesis, Luminescence and Host-Guest Chemistry of Mono- and Dinuclear Platinum(ii) Complexes of Pyridyl and Diphosphine Ligands written by Pui-Ling Tang and published by . This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Platinum(ii) Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen, Nitrogen and Carbon Donor Atoms and Platinum(ii)-Containing Phosphorescent Polymers by : Wai-Yip Tong
Download or read book Luminescent Platinum(ii) Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen, Nitrogen and Carbon Donor Atoms and Platinum(ii)-Containing Phosphorescent Polymers written by Wai-Yip Tong and published by Open Dissertation Press. This book was released on 2017-01-26 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Luminescent Platinum(II) Complexes Containing Dianionic Tetradentate Ligands Having Mixed Oxygen, Nitrogen and Carbon Donor Atoms and Platinum(II)-containing Phosphorescent Polymers: Synthesis, Photophysical Properties and Material Applications" by Wai-yip, Tong, 唐煒燁, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled LUMINESCENT PLATINUM(II) COMPLEXES CONTAINING DIANIONIC TETRADENTATE LIGANDS HAVING MIXED OXYGEN, NITROGEN AND CARBON DONOR ATOMS AND PLATINUM(II)-CONTAINING PHOSPHORESCENT POLYMERS: SYNTHESIS, PHOTOPHYSICAL PROPERTIES AND MATERIAL APPLICATIONS Submitted by TONG WAI YIP for the degree of Doctor of Philosophy at The University of Hong Kong in May 2014 Square planar platinum(II) complexes exhibit rich photophysical properties which are tunable through the structural variation of ligands and can be harnessed for applications in materials science. In this thesis, the great variety of spectroscopic properties of various square planar cyclometalated platinum(II) complexes supported by tetradentate (O DEGREESN DEGREESN DEGREESC and O DEGREESN DEGREESC DEGREESN) and tridentate (C DEGREESN DEGREESN) ligands containing dipyridyl moieties will be highlighted, along with their synthesis, characterization and potential application in organic light emitting diodes (OLEDs). Ind Platinum(II) complexes supported by tetradentate O DEGREESN DEGREESN DEGREESC or O DEGREESN DEGREESN DEGREESC types of ligands (O DEGREESN DEGREESN DEGREESC = 2-(4-(3,5-di-tert-butylphenyl)-6'-phenyl-2,2'- Ind bipyridin-6-yl)phenolate; O DEGREESN DEGREESN DEGREESC = 5,5-dialkyl-2-(6-phenylpyridin-2-yl) indeno[1,2-b]pyridin-9-olate) are emissive in solution at room temperature, with emission maxima tunable from 582 nm to 640 nm and quantum yields up to 0.28. Mechanochromism and the associated luminescence change in [Pt(dihexyl- Ind O DEGREESN DEGREESN DEGREESC)] (Complex 3.6) were found associated with the two different crystal packings revealed by powder X-ray diffraction (PXRD) studies. Fast vapochromic response of [Pt(3-O DEGREESN DEGREESN-2,6-difluoropyridine)] (Complex 3.3) on chloroform or dichloromethane vapours was found to be associated with structural changes in the solid state through PXRD studies. Robust and strongly emissive platinum(II) complexes supported by tetradentate O DEGREESN DEGREESC DEGREESN ligands featuring fused six-five-six membered metallacyclic ring (O DEGREESN DEGREESC DEGREESN = 2-(4-(3,5-di-tert-butylphenyl)-6-(9-(pyridin-2-yl) carbazol-2-yl)pyridin-2-yl)phenol) have been prepared. These platinum(II) complexes are among the most efficient yellow phosphors, with emission maxima ranging from 526 nm to 553 nm and luminescence quantum yields as high as -1 0.47-0.86. A yellow OLED with power efficiency (η ) up to 52 lm W is power demonstrated. In combination with the typical blue emitting iridium(III) 2' bis(4,6-difluorophenyl-pyridinato-N, C ) picolinate (FIrpic), white organic -1 light-emitting diodes (WOLEDs) displayed η up to 61 lm W and reduced power -2 efficiency roll-off at 1000 cd m . Random copolymers with photo-inert backbone poly[(N-vinylcarbazole)-co- ((R-C DEGREESN DEGREESN)Pt)] and poly[(2-(4-tert-butylphenyl)-5-(4-vinylphenyl)-1,3,4- oxadiazole)-co-((R-C DEGREESN DEGREESN)Pt)] (R-C DEGREESN DEGREESN = 3-(6-phenyl-4-(4-vinylphenyl) pyridine-2-yl)-isoquinoline or 3-(4-(4-(dec-9-enyloxy)phenyl)-6-phenylpyridin- 2-yl)isoquinoline) have been synthesized and characterized. Energy transfer between the charge transporting units and emissive (R-C DEGREESN DEGREESN)Pt units was revealed through ICP-MS inve
Book Synopsis Design, Synthesis and Functionalization of Luminescent Alkynylgold(I) Complexes with [pi]-conjugated Ligands by : 康祐軒
Download or read book Design, Synthesis and Functionalization of Luminescent Alkynylgold(I) Complexes with [pi]-conjugated Ligands written by 康祐軒 and published by . This book was released on 2015 with total page 315 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Luminescent Platinum(ii), Palladium(ii) and Gold(iii) Complexes Containing Isocyanide, Alkynyl and N-Heterocyclic Carbene Ligands by : Faan-Fung Hung
Download or read book Luminescent Platinum(ii), Palladium(ii) and Gold(iii) Complexes Containing Isocyanide, Alkynyl and N-Heterocyclic Carbene Ligands written by Faan-Fung Hung and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Luminescent Platinum(II), Palladium(II) and Gold(III) Complexes Containing Isocyanide, Alkynyl and N-heterocyclic Carbene Ligands: Synthesis, Photophysical Properties and Material Applications" by Faan-fung, Hung, 孔繁峰, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Several cyclometalated Pt(II) isocyanide complexes containing C-deprotonated C DEGREESN DEGREESC ligands (C DEGREESN DEGREESC = 2,6-diphenylpyridine derivatives) were synthesized. These complexes display orange-red emissions with max at 582-619 nm and quantum yields of up to 26% in CH2Cl2 at room temperature. The incorporation of carbazole/fluorene/thiophene unit(s) to C DEGREESN DEGREESC ligands leads to minimized structural distortion of complexes in their excited states and thereby suppresses non-radiative decay pathways. The high thermal stability (Td >300 C) renders these complexes good candidates as phosphorescent dopants in organic light-emitting diodes (OLEDs). Red-emitting OLEDs with CIE coordinates of (0.650.01, 0.350.01) were fabricated by vacuum deposition, showing a maximum external efficiency of 12%. In addition, well-defined nano/microstructures were obtained from self-assembly of these complexes driven by π∙∙∙π, C-H∙∙∙π and C-H∙∙∙H-C interactions as observed in the crystal structures. Two series of organopalladium(II) alkynyl complexes containing a terpy (terpy = 2,2':6',2''-terpyridine) or C DEGREESN DEGREESC pincer carbene ligand (C DEGREESN DEGREESC = 2,6-bis(1-butylimidazol-2-ylidenyl)pyridine) were prepared. These complexes are non-emissive in solution at room temperature except that the one containing both C DEGREESN DEGREESC and pyrenylacetylide ligands shows phosphorescence (Φ = 0.3%) originating from intraligand state of the acetylide ligand. This could be attributed to the strong -donating N-heterocyclic carbene (NHC) in the pincer ligand that strongly destabilizes d-d state, the population of which provides an efficient non-radiative decay channel. To make comparison between Pd(II) and Pt(II) complexes with the two ligand systems, Pt(II) C DEGREESN DEGREESC alkynyl complexes were also prepared. They are emissive in solution and some display excimer emissions at high concentration (〖10〗 DEGREES(-4)-〖10〗 DEGREES(-3) mol 〖10dm〗 DEGREES(-3)). The X-ray crystal structures of [Pd(L)(CCPh)](〖PF〗_6) (L = terpy and C DEGREESN DEGREESC) revealed one-dimensional chain stacking of complex cations with alternating Pd(II)∙∙∙Pd(II) contacts of about 3.29-3.35 A and π-π interactions of about 3.4 A . Well-defined submicron/nanostructures were obtained from self-assembly of Pd(II) and Pt(II) alkynyl complexes driven by π-π interactions between aromatic moieties and/or metal∙∙∙metal interactions. DFT calculations on the optimized structures of [M(L)(CCPh)]+ (M = Pd(II) and Pt(II)) revealed the existence of metal∙∙∙metal closed-shell interactions. In addition, the complex containing the C DEGREESN DEGREESC ligand exhibits slightly enhanced metal∙∙∙metal interactions and larger "bonding" energy upon dimerization. Furthermore, spin-orbit coupling between singlet and triplet excited states is more effective which promotes rapid intersystem crossing. A new class of cyclometalated Au(III) complexes containing C-deprotonated C DEGREESN ligands (C DEGREESN = 2-phenylpyridine and its derivatives) and cis-chelating bis-NHC ligands was synthesized. These are the first examples of Au(III) complexes supported by cis-chelating bis-NHC ligands. They display emissions in solution under degassed condition at room temperature with &
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