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    Insight into the Coordination Varieties of a NxO2 Peraza-Crown Macrocyclic Ligand Group Anchored by Pyridine Side Arms

    , Ph.D. Dissertation Sharif University of Technology Asadi Mofarrah, Leila (Author) ; Ghanbari, Bahram (Supervisor)
    Abstract
    In this treatise, the effect of type of macrocycle ring on the final structure of the complexes which made from them was investigated. For this purpose, by changing the 15-membered benzylic macrocycle with two pyridine pendant arms (2p), which was studied in our previous experiments (the effect of the position of the nitrogen atom of the pyridine ring in the side arm and the type of metal ion in the geometry of its complexes), two new macrocycles by adding a naphthalene rings instead of benzylic ringsin in 2p and increasing the ring size from 15 to 17 members, Lpy-naph and Lpy-benz were symthesized respectively. The molecular formula and structure of Lpy-naph and Lpy-benz were confirmed by... 

    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 Hendi, Zohreh (Author) ; 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 Dadkhahan, Leili (Author) ; 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 Multinuclear Platinum Complexes Containing Copper Group Metals and 2,6-Diphenylphosphinopyridin Bridging Ligand

    , M.Sc. Thesis Sharif University of Technology Akbarzadeh Khoei, Mahtab (Author) ; 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 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 Nayeri, Sara (Author) ; 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... 

    Study of Supramolecular Chemistry of Fullerene (C60) with Azobenzene Tweezer Linking to Biaza-Crown Macrocycles Coordinated to Zinc Tetraphenylporphyrin

    , M.Sc. Thesis Sharif University of Technology (Author) ; Ghanbari, Bahram (Supervisor)
    Abstract
    In this project, in continuation of a PhD resreach undertaken in this research group in 2017, the synthesis and study of two new tweezer and linker molecule bearing azobenzene moiety were carried out, characterized by applying IR spectroscopy, ¹H and ¹³C {¹H} NMR, fluorescence spectroscopy, UV-visible spectroscopy, elemental analysis and X-ray crystallography. Firstly, interaction of T2 with meso-tetraphenylporphyrinato zinc(II) and aluminium tetraphenylporphyrinato were studied using the fluorescence spectroscopy. The formation constant of T2 in cis and trans isomer with ZnTPP was measured as 5.1(±0.4) ×108 and 2.0×108(±1074) dm6mol-2, respectively. The formation constant of T2 in with... 

    Designing a New Ligand based on Pyridine for Immobilization of Gold Nanoparticles on Reduced Magnetic Graphene Oxide: A New Catalyst for the Reduction of Nitro Compounds and a Diastereoselective Construction of Functionalized Dihydro-Pyridazine based Spirooxindole Scaffold via C-3 Umpolung of Isatin N,N′-Cyclic Azomethine Imine

    , M.Sc. Thesis Sharif University of Technology Siahpoosh, Ali (Author) ; Matloubi Moghadam, Firouz (Supervisor)
    Abstract
    In this work, a new catalyst based on gold nanoparticles immobilized on magnetic GO (graphene oxide) has been introduced. A new ligand based on pyridine has been used to the functionalization of GO to design robust heterogeneous catalyst for reduction in a short time using a low amount of the catalyst. The prepared catalyst was employed in the synthesis of aromatic amines using various types of nitroarnes in water. This catalyst is readily prepared from available starting materials and also is a reusable catalyst having very good stability to air and moisture. The proposed procedure applied here can conduct the reactions under milder reactions. Finally, due to total removal of the... 

    Study of NxOy Macrocycles Bearing Peripheral Functional Groups as Axial Ligands of Zinc Tetraphenylporphyrin

    , M.Sc. Thesis Sharif University of Technology Barkhordari, Kimia (Author) ; Ghanbari, Bahram (Supervisor)
    Abstract
    In this project, M2 macrocyclic ligand, bearing three pyridine side arms (3p) was synthesized and characterized by employing elemental analysis and 1H NMR, 13C NMR and IR methods. The interaction of 3p with zinc tetraphenylporphyrin was investigated, using fluorescence and UV-vis spectroscopy in solution phase. The observed quenching in the fluorescence spectrum alongside Q band shift in UV-vis spectrum indicate on the interaction of 3p with ZnTPP. The formation constant for these interactions in 1:1 ratio was calculated 10100 M-1, employing fluorescence method. The formation constant was calculated 630 M-1 for 1:2 ratio for 3p:ZnTPP. Having 1:2 ratio 3pZnTPP was also synthesized and... 

    Synthesis, Characterization, Structure Determination and Theoretical Studies of Some New Dimethylglyoxime Cobalt (ΙII) Complexes

    , M.Sc. Thesis Sharif University of Technology Batmanghelich, Shiva (Author) ; Kia, Reza (Supervisor)
    Abstract
    In this study, a number of complex cobaloxim complexes [Co(DMG)2LX] in which L= 4-MePy, 3-MePy, 4-bzPy, 3-CNPy, 4-CNPy, tBuPy, styPy, NaphPy synthesized and their structure studied. These complexes were identified by FT-IR and 1H NMR methods as well as their solid state structure studied by X-ray crystallography of single crystals. Gaussian 09 software was used to optimize the geometric structure and obtain the vibrational frequency of cobalt complexes. Charge decomposition Analysis (CDA) and molecular orbital studies were performed using the AOMix 6.88 software. Also, the characterization of σ-donating and П-acceptoring of pyridine ligands in these complexes was investigated using... 

    Study on The Effect of Complex Formation of Pyridine-derivatized Aza-crown Macrocyclic Ligands Towards Zinc Tetraphenylporphyrin and Zinc Phthalocycnine, Cu(Ii) Cation and C60

    , Ph.D. Dissertation Sharif University of Technology Shah Hosseini, Leila (Author) ; Ghanbari, Bahram (Supervisor)
    Abstract
    A set of azacrown macrocyclic ligands bearing pyridine moiety (bp, 1p, 2p) were synthesized and characterized by single-crystal X-ray diffraction (SCXRD), elemental analysis, FT-IR, 1H and 13C NMR methods. The complexes of zinc tetraphenylporphyrin (ZnTPP) with the bp and 1p as the axial ligand were synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR, 1H and 13C NMR, fluorescence, UV-vis, cyclic voltammetry, together with TD DFT calculations. By employing this method for ZnTPPbenz and ZnTPPH complexes elucidated that the pyridine moiety was bonded through the fifth- coordination site on the zinc metal atom. In the following study, the coordination... 

    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 Naseri, Soroush (Author) ; 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... 

    2,6-Bis(diphenylphosphino)pyridine: A simple ligand showing high performance in palladium-catalyzed CN coupling reactions

    , Article Tetrahedron Letters ; Vol. 55, issue. 30 , July , 2014 , p. 4098-4101 ; ISSN: 00404039 Nadri, S ; Rafiee, E ; Jamali, S ; Joshaghani, M ; Sharif University of Technology
    Abstract
    The use of commercially available 2,6-bis(diphenylphosphino)pyridine as a ligand in conjunction with K2CO3, DMAc and TBAB is an effective method for the palladium-catalyzed CN coupling of a variety of aryl halides with anilines, N-heterocyclic aromatic amines, and a cyclic secondary amine. The reactions proceed in good to excellent yield (up to 98%) while the loading of Pd(OAc)2 was as low as 0.025 mol %  

    Facile synthesis of thiochromeno[2,3-b]indol-11(6H)-ones and pyrido[3′,2′:5,6]thiopyrano[2,3-b]indol-5(10H)-ones

    , Article Tetrahedron Letters ; Volume 54, Issue 37 , 2013 , Pages 5018-5021 ; 00404039 (ISSN) Kiamehr, M ; Moghaddam, F. M ; Semeniuchenko, V ; Villinger, A ; Langer, P ; Iaroshenko, V. O ; Sharif University of Technology
    2013
    Abstract
    Indole-2(3H)thiones were cyclized under the action of 2-fluorobenzoyl chlorides to give thiochromeno[2,3-b]indol-11(6H)-ones or under the action of 2-chloronicotinoyl chlorides to give pyrido[3′,2′:5,6]thiopyrano[2, 3-b]indol-5(10H)-ones. The reaction of cyclization proceeds regioselectively in DMF and does not require transition metals for completion. Obtained heterocycles are isosteric analogues of various tetracyclic indole derived alkaloids  

    Synthesis of a new class of tetronic acid derivatives: A one-pot three-component condensation reaction between isoquinoline or pyridine and dialkyl acetylenedicarboxylate with tetronic acid

    , Article Monatshefte fur Chemie ; Volume 144, Issue 7 , 2013 , Pages 1051-1055 ; 00269247 (ISSN) Rezayan, A. H ; Sabahi, H ; Rahmati, A ; Maleki, A ; Kheirjou, S ; Sharif University of Technology
    2013
    Abstract
    Reaction of the zwitterions generated from isoquinoline or pyridine and dialkyl acetylenedicarboxylate with tetronic acid leads to 1,2- dihydroisoquinoline or 1,2-dihydropyridine tetronic acid derivatives without using any catalyst or activation at room temperature  

    Activation of CX (=Cl, Br) bond in aryl halides toward the palladium-catalyzed Heck reaction using 2,6-bis(diphenylphosphino)pyridine

    , Article Journal of Molecular Catalysis A: Chemical ; Volume 366 , January , 2013 , Pages 30-35 ; 13811169 (ISSN) Ataei, A ; Nadri, S ; Rafiee, E ; Jamali, S ; Joshaghani, M ; Sharif University of Technology
    2013
    Abstract
    The 2,6-bis(diphenylphosphino)pyridine/palladium catalytic system successfully catalyzes the Heck coupling reaction of less reactive aryl chlorides as well as aryl bromides with styrene to give the corresponding olefins in reasonable yields. TBAB (tetrabutylammoniumbromide) as an additive was found to be essential for these reactions. The results of Heck reaction exhibited a high selectivity (>99/1) favoring the trans product  

    One-pot reductive amination of aldehydes by the dihydropyridine in water

    , Article Scientia Iranica ; Volume 19, Issue 6 , December , 2012 , Pages 1591-1593 ; 10263098 (ISSN) Ghafuri, H ; Hashemi, M. M ; Sharif University of Technology
    2012
    Abstract
    An efficient, highly chemoselective and simple synthesis of secondary amines via reductive amination of aldehydes, aromatic amines and inexpensive and easily accessible Diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (DHP) in the presence of catalytic amounts of p-toluenesulfonic acid (PTSA) in water in good to excellent yields is reported  

    Pyridinium salts - Versatile reagents for the regioselective synthesis of functionalized thiazocino[2,3-b]indoles by tandem dinucleophilic reactions of thiooxindoles

    , Article Tetrahedron ; Volume 68, Issue 47 , 2012 , Pages 9685-9693 ; 00404020 (ISSN) Kiamehr, M ; Moghaddam, F. M ; Gormay, P. V ; Semeniuchenko, V ; Villinger, A ; Langer, P ; Iaroshenko, V. O ; Sharif University of Technology
    2012
    Abstract
    The reaction of thiooxindoles with various 2- and 3-substituted pyridinium salts afforded a variety of functionalized thiazocinoindoles. The products have been prepared in good to excellent yields by regioselective dinucleophilic C/S-cyclocondensation of thiooxindoles with pyridinium salts  

    Monte Carlo sampling and multivariate adaptive regression splines as tools for QSAR modelling of HIV-1 reverse transcriptase inhibitors

    , Article SAR and QSAR in Environmental Research ; Volume 23, Issue 7-8 , Jun , 2012 , Pages 665-682 ; 1062936X (ISSN) Alamdari, R. F ; Mani Varnosfaderani, A ; Asadollahi Baboli, M ; Khalafi Nezhad, A ; Sharif University of Technology
    2012
    Abstract
    The present work focuses on the development of an interpretable quantitative structure-activity relationship (QSAR) model for predicting the anti-HIV activities of 67 thiazolylthiourea derivatives. This set of molecules has been proposed as potent HIV-1 reverse transcriptase inhibitors (RT-INs). The molecules were encoded to a diverse set of molecular descriptors, spanning different physical and chemical properties. Monte Carlo (MC) sampling and multivariate adaptive regression spline (MARS) techniques were used to select the most important descriptors and to predict the activity of the molecules. The most important descriptor was found to be the aspherisity index. The analysis of variance... 

    Synthesis and characterization of metal dithiocarbamate derivatives of 3-((pyridin-2-yl)methylamino)propanenitrile: Crystal structure of [3-((pyridin-2-yl)methylamino)propanenitrile dithiocarbamato] nickel(II)

    , Article Polyhedron ; Volume 102 , 2015 , Pages 643-648 ; 02775387 (ISSN) Halimehjani, A. Z ; Torabi, S ; Amani, V ; Notash, B ; Saidi, M. R ; Sharif University of Technology
    Elsevier Ltd  2015
    Abstract
    Four metal dithiocarbamate complexes (Zn, Ni, Hg and Sn) based on an amine containing pyridyl and nitrile groups, 3-((pyridin-2-yl)methylamino)propanenitrile, were prepared and characterized by their elemental analysis, spectroscopic data (such as IR, 1H and 13C NMR), TGA analysis and X-ray crystallography of the Ni(II) complex. The presence of a band in the 1000 cm-1 region in the IR spectra, without any splitting, confirms the symmetrical bidentate bonding mode of the dithiocarbamate ligand. Also, the short thioureide C=N distance in the X-ray analysis of the Ni complex confirms the delocalization of π electrons over the S2CN moiety and strong double bond character between the carbon and... 

    In situ forming interpenetrating hydrogels of hyaluronic acid hybridized with iron oxide nanoparticles

    , Article Biomaterials Science ; Volume 3, Issue 11 , Aug , 2015 , Pages 1466-1474 ; 20474830 (ISSN) Kheirabadi, M ; Shi, L ; Bagheri, R ; Kabiri, K ; Hilborn, J ; Ossipov, D. A ; Sharif University of Technology
    Royal Society of Chemistry  2015
    Abstract
    Four derivatives of hyaluronic acid (HA) bearing thiol (HA-SH), hydrazide (HA-hy), 2-dithiopyridyl (HA-SSPy), and aldehyde groups (HA-al) respectively were synthesized. Thiol and 2-dithiopyridyl as well as hydrazide and aldehyde make up two chemically orthogonal pairs of chemo-selective functionalities that allow in situ formation of interpenetrating (IPN) disulfide and hydrazone networks simultaneously upon the mixing of the above derivatives at once. The formation of IPN was demonstrated by comparing it with the formulations of the same total HA concentration but lacking one of the reactive components. The hydrogel composed of all four components was characterized by a larger elastic...