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

Barkhordari, Kimia | 2018

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  1. Type of Document: M.Sc. Thesis
  2. Language: Farsi
  3. Document No: 51562 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Ghanbari, Bahram
  7. Abstract:
  8. 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 characterized by elemental analysis and 1H NMR and 13C NMR spectra. In the presence of various metal ions, the intensity of the fluorescence spectrum of 3pZnTPP was examined, while a slight quenching was observed. In the course of the experiment, the most quenching phenomena was observed for Mn and Ag metal ions. Due to the six coordinating nature of Al in tetraphenylporphyrin, AlTPPCl was synthesized and was characterized by employing elemental analysis, UV-vis spectroscopy, 1H NMR and 13C NMR methods. The interaction of 3p with AlTPPCl was investigated in solution, using fluorescence and UV-vis spectroscopy and 1H NMR in solutions phase. Using fluorescence method, the formation constant of 3p/AlTPPCl in 1:1 ratio and 1:2 ratio for AlTPP:3p was calculated as indicating 2600 M-1 and 4400000 M-1, respectively. To investigate the effect of the macrocycle moiety on formation constant, having the same number of the pyridine groups, was investigated in the presence of zinc tetraphenylporphyrin. For this purpose, SP was synthesized and characterized by employing elemental analysis and 1H NMR, 13C NMR and IR methods. The interaction of SP with ZnTPP was determined by florescence method. Herein, the observed quenching in the emission indicated on the interaction of SP with ZnTPP. Furthermore, the formation constant for SP/ZnTPP was calculated 450 M-1, using fluorescence method. In a supplementary work, an acetate-bearing N2O2 azacrown macrocyclic ligand, MA1, together with its Cd complex was synthesized and characterized by single crystal X-ray crystallography
  9. Keywords:
  10. Macrocycle ; Porphyrin ; Pyridines ; Axial Ligand ; Tetraphenyl Porphyrin ; Functional Group

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