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Synthesis of Tweezer-Like OxNy Macrocyclic Ligands and Study on the Effect of Macroring Linking on Selectivity Towards [60]Fullerene and Transition Metal Cations

Gholamnezhad, Parisa | 2016

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  1. Type of Document: Ph.D. Dissertation
  2. Language: Farsi
  3. Document No: 48754 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Ghanbari, Bahram; Bagherzadeh, Mojtaba
  7. Abstract:
  8. By considering previous works undertaken in our laboratory on the interaction between O2N2 azacrown and [60]fullerene using UV-vis spectroscopy. It was found that the significant interaction occurs in less than one hour. Extending this time in this research, the reaction between [60]fullerene with 15 to 19 membered N2O2-azacrown macrocyclic ligands was investigated during ten days. The new compounds L1, L2 were synthesized and characterized applying HPLC, ESI-Mass, TG, DSC, IR as well as elemental analysis. The interaction of new compounds with Cu(II) and Ni(II) and Co(II) using UV-vis spectroscopy showed that L2 gave the highest Kb value of cations/(L1, L2). Besides, it was found that the incorporation of [60]fullerene into these macrocyclic ligands resulted in enhancement of their thermodynamic stability. The interaction of 15 to 19 membered macrocycles containing an O2N2-donor set has been investigated by UV-vis spectroscopy. The calculated Kb obtained by the Benesi–Hildebrand equation showed a "saw-tooth" pattern. Furthermore 4 showed the highest Kb value for these Cu(II) O2N2-azacrown (1–5) complexes. By introducing of pyridine arm to 15 membered N2O2 macrocyclic ligand, the new compounds 1-benz-Py and 1-benz-Py-Pd were synthesized and characterized applying 1H, 13C{1H} NMR, IR and as well as elemental analysis. The interaction of these new compounds with [60]fullerene and Cu(II) using UV-vis spectroscopy showed that the incorporation of pyridine arm into these macrocyclic ligand resulted in enhancement of their thermodynamic stability for supramolecular interaction of [60]fullerene with these new compounds, while the results for Cu(II) represented little change. Furthermore the new compounds 1-Naph-Py and 1-Naph-Py-Pd were synthesized and characterized applying 1H,13C{1H} NMR as well as elemental analysis. The interaction of these new compounds with [60]fullerene and Cu(II), Zn(II) and Hg(II) using UV-vis and fluorescence spectroscopy showed that the new compounds gives the highest Kb value for [60]fullerene. Finally, the tweezer moleculars Pd-N-N-Pd and 1-Naph-Py-Pb were synthesized and characterized. The results of interaction of 1-Naph-Py-Pb with [60]fullerene as well as Cu(II), Hg(II) and Zn(II) using fluorescence spectroscopy confirmed on a static mechanism supramolecular interaction between 1-Naph-Py-Pb and [60]fullerene with Kb= 470000(±186) M-1
  9. Keywords:
  10. Fullerene ; Macrocyclic Ligand ; Spectrofluorometry ; Tweezer ; Electron Spectroscopy ; Binding Constant

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