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Synthesis and Characterization of Heterobinuclear Cyclometalated Complexes Containing Small Bite Angle Bridging Ligand
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The heteronuclear complexes [MePt(bhq)(μ-dppy)Au(PPh3)]PF6, 2, [MePt(bhq)(dppy)Tl]PF6, 3 and [Me2Pt2(bhq)2(dppy)2Tl]PF6, 4 in which bhq=benzo{h}quinoline and dppy=2-diphenylphosphinopyridine, were prepared by reaction of the mononuclear complex [MePt(bhq)(dppy)] 1 with 1 equivAuCl(PPh3), 1equiv TlPF6 and 1/2 equiv TlPF6 respectively. All the complexes were fully characterized using multinuclear NMR spectroscopy and ESI-MS spectrometry. In addition molecular structures of complexes 2 and 3 in solid state have been determined by X-ray crystallography that shown strong dative bonds between platinum and gold or thallium atoms. As shown by ESI-MS spectrometry, the Pt-Au bond in complex 2...
Synthesis, Characterization and Photophysical Study of Cationic Cyclometalated Platinum Complexes Containing 2-Phenylpyridine Ligand and its Derivatives
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The cationic cyclometalated platinum(II) complex [Pt(ⱪ2-2-ppy)(ⱪ1-N-2-ppy)2][OTF], 2, has been prepared by reaction of [PtMe3I]4, 1, with one equiv Ag(OTF) and then three equiv 2-phenylpyridine. The similar complex with formula [Pt(ⱪ2-p′py)(ⱪ1-N-p′py)2][OTF], in which p′py = 2-(3-bromophenyl)pyridine, 4, has been prepared with similar procedure, from the reaction of 1 with one equiv Ag(OTF) and then three equiv of the corresponding cyclometalating ligand. Also, the cationic cyclometalated platinum(IV) complex [Pt(2-(p-tolyl)pyridine)2(Me)(H2O)][OTF], 3, has been prepared from the reaction of 1 with one equiv Ag(OTF) and then three equiv 2-(p-tolyl)pyridine. The structure of complexes 2, 3...
Synthesis, Characterization and Emission Study of Bis-cyclometalated Platinum(II) Complexes Containing 2-Phenylpyridine Ligand and its Derivatives
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The bis(cyclometalated) platinum(II) complexes of the type [Pt(ppy)(p′py)], in which ppy = p′py = 2-(p-tolyl)pyridine, 6; ppy = 2-(3-bromophenyl)pyridine, p′py = 2-(p-tolyl)pyridine, 7; ppy = 2-(2,4-difluorophenyl)pyridine, p′py = 2-(p-tolyl)pyridine, 8; ppy = 2-(2,4-difluorophenyl)pyridine, p′py = 2-(2,4-difluorophenyl)pyridine, 9, have been prepared from the reaction of the cyclometalated platinum(II) complex [Pt(ppy)Me(SMe2)] with one equiv p′py and one equiv B(C6F5)3. The structure of 6, 7 and 10 determined using X-ray crystallography in solid state. However NMR spectroscopy methods have been used for structural characterization of the complexes in solution phase. The bis(cyclometalated)...
Synthesis, Characterization and Optical Study of a New Heterobinuclear Bis(Cyclometalated) Complex Containing Pt(II) and Au(I)
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The bis-cyclometalated platinum(II) complexes [Pt(ptpy)2], 3, and [Pt(fppy)2], 4, in which, ptpy = 2-(p-tolyl)pyridine and fppy = 2-(2,4-difluorophenyl)pyridine have been prepared. The reaction of 3 with one equiv [Au(PPh3)]+ (prepared from the reaction between AuCl(PPh3) and AgOTf) gave the heterobinuclear complex [Pt(ptpy)2Au(PPh3)].OTf, 5, by formation of a Pt→Au dative bond. The structure of all complexes were characterized using multinuclear NMR spectroscopy in solution phase and the structures of 4 and 5 determined using X-ray crystallography in solid state. The structure of heterobinuclear complex 5 shows an unusual Pt-Au bond that supported by Au-Cipso bond. The absorption and...
Synthesis and Study of Emission Properties Of Binuclear Platinum and Silver Complexes by Bridging Ligands of Phthalazine and Bis (Diphenylphosphino) Methane
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
Silver(I) complex of [Ag2(μ-dppm)2(μ-phth)(phth)](BF4)2 (1) (dppm = bis(diphenylphosphino)methane and phth = phthalazine) has been prepared from the reaction of [Ag(CH3CN)4]BF4 with phthalazine and dppm in a 1:1 molar ratio. The structure of 1 was determined using X-ray crystallography in solid state and by multinuclear NMR spectroscopy in solution. Complex 1 shows a dynamic process including rotation of phthalazine ligand around the [Ag2(μ-dppm)2] unit wich was investigated by 1H NMR, 31P NMR and 13C NMR spectroscopy. Also, the complex 1 shows the aggregation induced emission (AIE) probably by restriction of internal motions (RIM). The trimethyl platinum(IV) complex [PtMe3(phth)3]+X- (2)...
Synthesis of Homo and Hetero Bi and Multinuclear Complexes Containing Gold and Closed-Shell Metals Using Bridging Phosphine and Pyridine Ligands and Study of Their Emission Properties
, Ph.D. Dissertation Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In this project, multi-nucleated clusters of copper (I)-gold (I) and silver (I)-gold (I) were synthesized. Initially, two tetranuclear Au2Cu2 cluster complexes [Au2Cu2(μ-(PPh2)2py)2(μ-OH)](PF6)3, and [Au2Cu2Cl2(μ-(PPh2)2 py)2](OTf)2, have been prepared by the reactions of precursor complexes [Au2(μ-(PPh2)2py)2](OTf)2, and [Cu2(μ-(PPh2)2py)2(μ-SMe2)(OTf)2], with [Cu(NCCH3)4]PF6 and AuCl(SMe2), respectively. The crystal structures of two clusters were determined by X-ray crystallography, indicating a butterfly-shaped Au2Cu2 metal core for the first and a planar-shaped Au2Cu2 metal core for second cluster. In the first cluster, the Cu atoms occupy the edge-sharing bond, while in the second...
Design and Synthesis of the Late Transition Metal Complexes Based on Naphthalimide and Pyridine Ligands and Study of their Photophysical Properties
, Ph.D. Dissertation Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In the first project, we have described the preparation of quadruply linked naphthalimide compounds 3-6. These compounds showed weak and strong excimeric emissions in solid and solution states, respectively. The experimental and theoretical results showed that the adjacent naphthalimide rings were oriented in solution so that intramolecular interchromophoric interactions enhanced the quantum yield efficiencies. However, although the strong intramolecular π and solute-solvent interactions in solution were replaced by n→π*, inter- and intramolecular π-interactions in the solid state, the naphthalimide units were aligned so that the quantum yield efficiencies were diminished. Also, a rise in...
Synthesis and Characterization of Multinuclear Platinum Complexes Containing Copper Group Metals and 2,6-Diphenylphosphinopyridin Bridging Ligand
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In the current study, we prepared two new tetranuclear clusters with linear and nonlinear Pt2Ag2, Pt2Au2, and Pt2Cu2 metal cores.First, the tetranuclear cluster [Ag2Pt2(μ-Cl)2(bhq)2(μ-(PPh2)2py)2](OTf)2, 1, from the reaction of 1 equivalent of Pt(bhq)Cl(SMe2), with 1 equivalent of AgOTf and μ-(PPh2)2py ligand has been prepared.Secondly, the tetranuclear cluster [Au2Pt2(μ-(PPh2)2py)2(Cl)2(bhq)2](PF6)2, 3, by the reaction of 1 equivalent of the mononuclear complex [Au(μ-(PPh2)2py)2]PF6 with 1 equivalent of PtbhqClSMe2 and (PPh2)2py ligand has been prepared.The third complex [Cu2Pt2(μ-Cl)2(bhq)2(μ-(PPh2)2py)2](OTf)2 has been prepared by the reaction of 1 equivalent of AgOTf and CuBrSMe2 with...
Synthesis and Characterization of a New Metallomacrocycle Complex of Au(I) Containing 4,4ˊ-Azopyridine Ligand
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
Gold(I) complex of [Au2(μ-PAnP)Cl_2] (1) (PAnP = 9,10-bis(diphenylphosphino)anthracene) has been prepared from the reaction of AuCl(SMe2) with PAnP in a 2:1 molar ratio. The structure of 1 was determined using 1H NMR and 31P{1H} NMR spectroscopy in solution. The tetranuclear metallomacrocycle [Au4(μ-PAnP)2 (μ-4,4 AzoPy)2]OTf4 (2) (4,4 AzoPy = 4,4-Azopyridine) has been prepared from the reaction of complex 1 with AgOTf and 4,4-Azopyridine in a 1:2:1 molar ratio. The structure of 2 was characterized using X-ray crystallography in solid state, 1H NMR and 31P{1H} NMR spectroscopy, UV-Vis spectroscopy and photoluminescence spectroscopy in solution state. The 1 has bright green emission in solid...
Synthesis, Characterization and Emission Study of Carbazole-Based Platinum(II) Pincer Complexes and their Emission Properties
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
Platinum(II) complex [Pt(Carb-PPh2)Cl] (1) (Carb-PPh2 = 1,8-bis(phosphino)-3,6-di-tert-butyl carbazole) was synthesized from the reaction of K2[PtCl4] salt with PNP carbazole-based pincer ligand, 1,8-bis(phosphino)-3,6-di-tert-butyl carbazole (c) and LiHMDS in a 1:2:1.1 molar ratio. The structure of 1 was characterized by X-ray crystallography in solid state, NMR spectroscopy, UV-Vis spectroscopy, and photoluminescence spectroscopy in solution state. Platinum(II) complex [Pt(Carb-PPh2)(C≡CPh)] (2) was prepared from the reaction of complex 1 with phenylacetylene with a 3:1 molar ratio in the presence of CuI as a catalyst and triethylamine. Complex 2 was identified by NMR spectroscopy, UV-Vis...
Synthesis and Characterization of New Bis(N-heterocyclic) Carbene Platinum (II) Complexes: Study of Stability and Reactivity in C-H Activation
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
Preparation of two new Bis-N-heterocyclic carbene (Bis-NHC) platinum (ІІ) complexes have been described. The reaction of the Bis-NHC complex [PtMe2(Bis-NHC)], 1, in which Bis-NHC = 1,1’-methylene-3,3’-di(tert-Bu)imidazole ylidene, with two equivalent trifluoroacetic acid give the new Bis-NHC platinum [Pt(Bis-NHC)(CF3COO)2], 2. Complex 2 has been characterized by multinuclear NMR spectroscopy in solution and its solid state structure determined using X-ray crystallography. The mono-methyl Bis-NHC platinum(ІІ) complex, {PtMe(Bis-NHC)[OHB(C6F5)3]}, 3, has been prepared by the reaction of one equivalent B(C6F5)3 with [PtMe2(Bis-NHC)], 1. The mono-methyl complex 1 has a labile ligand...
Synthesis of Ligand Containing Azulene Group by Cross Coupling and Study of Complexation with Late Transition Metals
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In this study the azulene-based ligand 2-(2-pyridylazulene) has been prepared by the coupling reaction between 2-bromopyridine and 2-(2_(6methyl azulene)) -4,4,5,5 tetra methyl-1,3,2- dioxaborolane in the presence of Palladium catalyst, [PdCl2(PPh3)2] .This ligand completely characterized by one and two dimentional NMR spectroscopy and its structure determined using X-ray crystallography method. The reaction of this ligand with 0.5 equivalent of Copper (Ⅰ) or Gold (Ⅰ) metal precursors, [Cu(CH3CN)4]PF6 or [Au(SMe2)Cl] gave the mononuclear Copper (Ⅰ) complex, [Cu (2-(2-pyridyl)6-methylazulene)2]PF6, 1 or Gold (Ⅰ) complex, [Au(2-(2-pyridyl)6-methylazulene)2], 2 respectively. Complexes 1 and 2...
Synthesis, Characterization and Emission Properties of Unsupported Heteronuclear Pt/Au and Pt/Tl Complexes
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The preparation and optical properties of two new unsupported Pt/Au and Pt/Tl heteronuclear complexes have been described.The heterobinuclear complexe [(tBu3P)2Pt-Au(PPh3)], 2, has been synthesized from reaction of the cluster complex {[(PPh3)Au]3(µ-O)}BF4 with 3 equiv [(tBu3P)2Pt] and characterized by multinuclear NMR spectroscopy in solution and using X-ray crystallography in the solid state. The tetranuclear linear chain cluster [(tBu3P)2PtTl2Pt(tBu3P)2](PF6)2, 3,has been prepared from the reaction of platinum(0) complex [(tBuP)2Pt] with 1 equiv TlPF6 in dry acetone. Complex 3 shows strong red emission with 73% quantum yield. DFT and TD-DFT calculations show that the emission originated...
Synthesis and Photophysical Study of Heterobinuclear Cyclometalated Pt-Au Complexes
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The cyclometalated heterobinuclear platinum-gold complexes [PtMe(bhq)(dppy)AuCl], 2, and [PtMe(bhq)(dppy)Au(NHC1)] PF6, 3, in which bhq= benzo{h}quinoline, dppy = 2-diphenylphosphinopyridine and NHC1 = 1,3-dimethylimidazol-2-ylidine have been prepared by reaction of the cyclometalated platinum complex [PtMe(bhq)(dppy)], 1, with 1 equivalent of AuCl(SMe2) or 1 equivalent of [Au(NHC1)]+ (prepared from ClAu(NHC1) and AgPF6), respectively. Complexes 2 and 3 were fully characterized using multinuclear NMR spectroscopy (1H, 31P). However complex 2was further characterized by x-ray crystallography, crystallization of complex 3 leads to form anew dimer complex 4,[Pt2(bhq)2(-dppy)2]2(PF6)2. The NMR ...
Synthesis and Characterization of Cyclometalated Platinum Complexes Containing 2-Vinylpyridine Ligand
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The cyclometalated platinum(II) complex [Pt(Me)(bhq)(2-vpy)], 2, in which bhq = benzo{h}quinolone, 2-vpy = 2-vinylpyridine, has been prepared by reaction of the cyclometalated complex [Pt(Me) bhq)(SMe2)], 1 with one equiv 2-vinylpyridine. The similar complex [Pt(p-tolyl)(ppy)(2-vpy)], 3 in which ppy = 2-phenyl pyridine, has been prepared from reaction of the platinum(II) complex cis-[Pt(p-MeC6H4)2(SMe2)2] with one equiv 2-phenylpyridine and one equiv 2-vinylpyridine. Reaction of 2 with one equiv Br2 in acetone gave the cyclometalated platinum(IV) complex [Pt(bhq)Me(Br)(NC5H4CHCH2Br)], 4. The structure of the complexes 1-3 were determined using NMR Spectroscopy. The crystal structure of 3...
Synthesis, Characterization and Study of the Optical Properties of Gold(I) Complexes Bearing Vinyl Pyridine and 1,8-Naphtyridine Ligands
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
The reaction of AuCl(SMe2) with two equiv of 2-vinylpyridine(2-Vpy) and one equiv of AgOTf gave the gold(I) complex [Au(2-Vpy)2], 1. Also the cationic gold(I) complex [Au(1,8-Naph)2][NTf2], 2, in which NTf2 is Bis(trifluoromethanesulfonyl)imide, has been prepared from the reaction of AuCl(SMe2), two equiv 1,8-naphthyridine and one equiv Ag(NTf2). The partial replacement of the NTf2 counter ion by PF6 using the reaction of 2 with one equiv TlPF6 leads to formation of the gold(I) complex [Au(1,8-Naphthyridine)2]〖"[NTf2]" 〗_("1" ⁄"3" ) 〖"[PF6]" 〗_("2" ⁄"3" ), 3. The solid state structure of 3 was determined using X-ray crystallography and its optical properties have been studied at room...
Study of the Optical Properties and Structural Fluxionallity of a New Cu(I) Complex Containing Bis(diphenylphosphino)methane and Phthalazine
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In the current study, the dinuclear copper(I) complex ,[Cu2(μ-phthalazine)(phthalazine)2(μ-dppm)2](PF6)2,(1), has been prepared by the reaction of two equiv of [Cu(CH3CN)4]PF6, three aquiv of phthalazine, and two equiv of bis(diphenylphosphino)methane (dppm). However a mixture of two four coordinated copper(I) complex,1, and a three and four-coordinated copper(I) complex ,[Cu2(μ-phthalazine)(phthalazine)(μ-dppm)2](PF6)2,(2), have been prepared when the reaction has been carried out with equal ratio of the reactants. The structure of 1 and 2 determined using. X-ray crystallography in solid state and the structure of 1, further characterized by multinuclear NMR spectroscopy in solution....
Synthesis and Characterization of Multinuclear Platinum Complexes Containing Copper Group Metals and 2,6-Diphenylphosphinopyridin Bridging Ligand
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In this project, we prepared two new tetranuclear clusters with linear Pt2Ag2 and Pt2Au2 metal cores. First, The tetranuclear cluster [Ag2Pt2(Cl2)(bhq2)(μ-(PPh2)2py)2](OTf)2, 1, from the reaction of 1 equivalent of Pt(bhq)Cl(SMe2), with 1 equivalent of AgOTf and μ-(PPh2)2py ligand has been prepared. Secondly, the tetranuclear cluster [Au2Pt2 (μ-(PPh2)2py)2(Cl2)(bhq2)]( PF6 )2, 3, by the reaction of 1 equivalent of the mononuclear complex [Au(μ-(PPh2)2py)2]PF6 with 1 equivalent of PtbhqClSMe2 and μ-(PPh2)2py ligand has been prepared. Structure of complexes has been fully characterized in solution, solid and gas states using multinuclear NMR spectroscopy, X-ray crystallography and ESI-MS...
Synthesis, and Characterization of Binuclear Platinum (IV)with Coinage Metals
, M.Sc. Thesis Sharif University of Technology ; Jamali, Sirous (Supervisor)
Abstract
In this research binuclear platinum(IV) complexes with coinage metals have been synthesized and characterized. the trimethyl platinum(IV) complex [PtMe3(phthalazine)3]+X- has been prepared by the reaction of [PtMe3(THF)]4 with 3 equiv. phthalazine and used as initial material. The first complex, [PtMe3(µ-(phthalazine)2Cl)PtMe3], synthesized via reaction of 2 equiv. [Pt(Me)3(Phthalazine)3] with 1 equiv. [AuClSMe2]. The second complex, [PtMe3(µ-phthalazine)3Ag][BF4], synthesized by reaction of one equiv. of each compound [Ag(CH3CN)4]BF4 and [Pt(Me)3(Phthalazine)3] And the third complex, [PtMe3(µ-phthalazine)3Cu][PF6], synthesized like second one via reaction of [Cu(CH3CN)4]PF6 and...
Synthesis and Catalytic Activity of Mo(VI) Oxo-peroxo Complex in Selective Oxidation of Sulfides to Sulfoxides and Alkenes to Epoxides
, M.Sc. Thesis Sharif University of Technology ; Bagherzadeh, Mojtaba (Supervisor) ; Jamali, Sirous (Co-Advisor)
Abstract
Considerable efforts have been directed in recent years towards the transition metal complex catalyzed oxidation of organic compounds. Among these, oxidation of sulfides to sulfoxides and alkenes to epoxides have specially been attended a lot, since sulfoxides and epoxides are important intermediates in organic synthesis. In this study [MoO(O2)(oxazine)2] complex has been synthesized and characterized by FT-IR and 1HNMR. This complex was found to be an efficient, selective catalyst for the oxidation of various sulfides to sulfoxides with urea hydrogen peroxide (UHP) in excellent yields (100% for dioctylsulfide) and short reaction times (20 min) at room temperature. Also this new efficient...