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    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... 

    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... 

    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... 

    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... 

    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... 

    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 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... 

    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 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... 

    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... 

    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... 

    Chemometrics comparison of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry Daphnia magna metabolic profiles exposed to salinity

    , Article Journal of Separation Science ; Volume 41, Issue 11 , 2018 , Pages 2368-2379 ; 16159306 (ISSN) Parastar, H ; Garreta Lara, E ; Campos, B ; Barata, C ; Lacorte, S ; Tauler, R ; Sharif University of Technology
    Wiley-VCH Verlag  2018
    Abstract
    The performances of gas chromatography with mass spectrometry and of comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry are examined through the comparison of Daphnia magna metabolic profiles. Gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with mass spectrometry were used to compare the concentration changes of metabolites under saline conditions. In this regard, a chemometric strategy based on wavelet compression and multivariate curve resolution–alternating least squares is used to compare the performances of gas chromatography with mass spectrometry and comprehensive two-dimensional gas chromatography with... 

    PH-Sensitive stimulus-responsive nanocarriers for targeted delivery of therapeutic agents

    , Article Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology ; Volume 8, Issue 5 , 2016 , Pages 696-716 ; 19395116 (ISSN) Karimi, M ; Eslami, M ; Sahandi Zangabad, P ; Mirab, F ; Farajisafiloo, N ; Shafaei, Z ; Ghosh, D ; Bozorgomid, M ; Dashkhaneh, F ; Hamblin, M. R ; Sharif University of Technology
    Wiley-Blackwell  2016
    Abstract
    In recent years miscellaneous smart micro/nanosystems that respond to various exogenous/endogenous stimuli including temperature, magnetic/electric field, mechanical force, ultrasound/light irradiation, redox potentials, and biomolecule concentration have been developed for targeted delivery and release of encapsulated therapeutic agents such as drugs, genes, proteins, and metal ions specifically at their required site of action. Owing to physiological differences between malignant and normal cells, or between tumors and normal tissues, pH-sensitive nanosystems represent promising smart delivery vehicles for transport and delivery of anticancer agents. Furthermore, pH-sensitive systems... 

    Calixarene based ionic liquid as an efficient and reusable catalyst for one-pot multicomponent synthesis of polysubstituted pyridines and BIS-pyridines

    , Article ChemistrySelect ; Volume 4, Issue 19 , 2019 , Pages 5903-5910 ; 23656549 (ISSN) Alishahi, N ; Mohammadpoor Baltork, I ; Tangestaninejad, S ; Mirkhani, V ; Moghadam, M ; Kia, R ; Sharif University of Technology
    Wiley-Blackwell  2019
    Abstract
    In this work, a calixarene based ionic liquid was successfully prepared and characterized by different techniques. This ionic liquid was used as an efficient catalyst for the synthesis of a series of polysubstituted pyridines from aldehydes, malononitrile, 1,3-diketones and arylamines in water as a green solvent. Also, for the first time, symmetric and unsymmetric polysubstituted bis-pyridines were obtained in high yields from diamines using this catalyst. Mild reaction conditions, high to excellent yields, easy work-up, excellent activity and reusability of the catalyst are the key features of this method which make it an interesting and novel alternative for the synthesis of the above... 

    PEG-co-polyvinyl pyridine coated magnetic mesoporous silica nanoparticles for pH-responsive controlled release of doxorubicin

    , Article International Journal of Polymeric Materials and Polymeric Biomaterials ; Volume 64, Issue 11 , 2015 , Pages 570-577 ; 00914037 (ISSN) Pourjavadi, A ; Mazaheri Tehrani, Z ; Bennett, C ; Sharif University of Technology
    Taylor and Francis Inc  2015
    Abstract
    In the present work a pH responsive drug nanocarrier based on magnetic mesoporous silica nanoparticles (MMSN) and polyethylene glycol-co-polyvinyl pyridine (PEG-co-PVP) was prepared. The core-shell nanocarrier was formed due to electrostatic interaction between protonated polyvinyl pyridine and surface modified MMSN with carboxylate groups. This carrier was used for pH-controllable doxorubicin release. The maximum release was occurred at pH 5.5 (pH of endosomes). This carrier was characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, UV-Vis spectrophotometer, scanning electron microscope, and high-resolution transmission electron microscope techniques. Also the... 

    N-doped CNT nanocatalyst prepared from camphor and urea for gas phase desulfurization: experimental and DFT study

    , Article Journal of the Taiwan Institute of Chemical Engineers ; Volume 85 , April , 2018 , Pages 121-131 ; 18761070 (ISSN) Ghasemy, E ; Banna Motejadded, H ; Rashidi, A ; Hamzehlouyan, T ; Yousefian, Z
    Taiwan Institute of Chemical Engineers  2018
    Abstract
    In the present work, mesoporous nitrogen-doped carbon nanotubes (N-CNTs) were synthesized by using a low-cost and unique set of precursors (camphor and urea). The CVD method at 1000 °C was used with different camphor/urea ratios, and Co-Mo/MgO nanocatalyst was utilized as growth catalyst. Application of mesoporous N-CNTs in selective oxidation of H2S was studied experimentally and N-CNTs interactions with H2S was also investigated using DFT calculations. The as-synthesized N-CNTs were characterized using FTIR, FE-SEM, elemental analysis, X-ray diffraction (XRD), XPS and nitrogen adsorption/desorption. The N-CNT2 sample with urea to camphor ratio (U/C) of 1 showed the highest sulfur yield at... 

    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... 

    Regiochemistry of nucleophilic substitution of pentachloropyridine with N and O bidentate nucleophiles

    , Article New Journal of Chemistry ; Volume 39, Issue 6 , 2015 , Pages 4398-4406 ; 11440546 (ISSN) Poorfreidoni, A ; Ranjbar Karimi, R ; Kia, R ; Sharif University of Technology
    Royal Society of Chemistry  2015
    Abstract
    Site reactivity of some enol-imines derived from N-aryl formamides with pentachloropyridine under basic conditions in dry CH3CN was investigated. The aromatic nucleophilic substitution of pentachloropyridine with enol-imines occurs at the 4-position of pyridine ring by both oxygen and nitrogen site of enol-imines. Nucleophilic attack by the oxygen of enol-imine gave corresponding oximino compounds as a mixture of E- and Z-isomers. In contrast, nucleophilic attack by the nitrogen of enol-imine gave the unexpected N,N-di-substituted aryl compounds. The structures of all the compounds were confirmed by IR, 1H NMR, 13C NMR and 19F NMR spectroscopy as well as elemental analysis and... 

    A cooperative pathway for water activation using a bimetallic Pt0-CuI system

    , Article Dalton Transactions ; Volume 45, Issue 44 , 2016 , Pages 17644-17651 ; 14779226 (ISSN) Jamali, S ; Abedanzadeh, S ; Khaledi, N. K ; Samouei, H ; Hendi, Z ; Zacchini, S ; Kia, R ; Shahsavari, H. R ; Sharif University of Technology
    Royal Society of Chemistry  2016
    Abstract
    A mixture of the platinum(0) complex [Pt(PtBu3)2] and tetrakis(acetonitrile)copper(i) hexafluorophosphate in acetone activated a water molecule and gave the hydride platinum(ii) complex [PtH(CH3CN)(PtBu3)2]PF6, 1, and the hydroxide Cu(i) species. The crystal structure of complex 1 was determined by X-ray crystallography, indicating a distorted square planar geometry around the platinum center. Although three possible mechanisms are proposed for this transformation, monitoring of the reaction using NMR spectroscopy at low temperature reveals that a cooperative pathway involving formation of a Pt0-CuI dative bond complex is the most probable pathway. The hydride platinum complex 1 is stable in... 

    Reactivity studies of biomimetic catalytic epoxidation of alkenes with tetrabutylammonium periodate in the presence of various manganese porphyrins and nitrogen donors: Significant axial ligand π-bonding effects

    , Article New Journal of Chemistry ; Volume 28, Issue 6 , 2004 , Pages 740-747 ; 11440546 (ISSN) Mohajer, D ; Karimipour, G ; Bagherzadeh, M ; Sharif University of Technology
    Royal Society of Chemistry  2004
    Abstract
    Highly selective epoxidation (> 95%) of unfunctionalized alkenes was performed by tetrabutylammonium periodate in the presence of six different phenyl substituted manganese(III) meso-tetraphenylporphyrins [Mn(Por)] and imidazole in CH2Cl2. Electron-withdrawing and bulky substituents on the phenyl groups lowered the catalytic activities of the corresponding Mn(Por). Less bulky alkenes with electron -rich double bonds showed greater reactivity in the epoxidation. Co-catalytic activities of four different classes of axial nitrogen donors are compared in the presence of various Mn(Por). In general no direct correlation was found between co-catalytic activities and the pKa values of the nitrogen...