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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

Shah Hosseini, Leila | 2018

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  1. Type of Document: Ph.D. Dissertation
  2. Language: Farsi
  3. Document No: 51306 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Ghanbari, Bahram
  7. Abstract:
  8. 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 chemistry of the new diaza-macrocycle bearing two pyridine side arms ligand (2p) with some transition metals and Pb were investigated. 2p showed a great tendency to act as an appropriate tecton in formation of coordination polymer in the presence of Cu, Ni, Mn, Pb, and Cd chlorides. Five new isostructural one dimensional metal–organic coordination polymers [{M(Cl)2}(L)4] (M = Cu, Ni, Mn, Pb, Cd) were prepared in DMSO or DMF and characterized by IR spectroscopy, TGA-DTG, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. All of the polymers were employed as solid sorbents for Cr(VI) anion in aqueous solution. Within the series, Pb(II) coordination polymer demonstrated notable absorption behavior for sorbent of Cr(VI) (99/4% in 60 min) with the maximum adsorption capacity of 28 mgchromate g−1adsorbent. Ni(II)-one dimensional coordination polymer (Ni(II)-Cp) and C60 coated glassy carbon electrode (GC) was successfully employed as a new non-enzymatic sensor for glucose. The Ni(II)-Cp/C60/GC electrode exhibited a high sensitivity of 614 AmM−1cm−2, low detection limit of 8.1 M as well as a typical response time of 5-10 s. The complexes of 2p with Pd(II) showed the 32-membered macrocyclic dinuclear palladium ring (Pd2L2Cl4) that was characterized by elemental analysis, IR, NMR spectroscopy and single crystal X-ray diffraction methods. Pd2L2Cl4 was investigated as a moisture/air-stable catalyst for Sonogashira cross-coupling reaction in the absence of copper and phosphine ligand in DMSO. In another study two new Fullerene derivative containing 17- and 19-membered O2N3-donor aza-crowns anchored to Fullerene were synthesized and characterized by employing HPLC, electrospray ionization mass (ESI-MS), 1H and 13C NMR, IR spectroscopies together with powder x-ray diffraction (PXRD) and thermogravimetric analysis (TGA) in solid state. Then, the ground state non-covalent interactions of Fullerene derivatives of O2Nx (x=2, and 3) aza-crown macrocyclic ligands namely, L1-L4 with zinc phthalocyanine (ZnPc) were also investigated by UV–vis absorption and steady state fluorescence spectrophotometry in N-methyl-2-pyrrolidone (NMP). The binding constants (KBH) of L1-L4/ZnPc were also determined applying the fluorescence quenching experiments
  9. Keywords:
  10. Azacrown ; Fullerene ; Complexation ; Phthalocyanin ; Tetraphenyl Porphyrin ; Macrocyclic Ligand ; Azacrown Macrocycle with Pyridine Arms ; Coordination Polymer

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