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

| 2019

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  1. Type of Document: M.Sc. Thesis
  2. Language: Farsi
  3. Document No: 51894 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Ghanbari, Bahram
  7. Abstract:
  8. 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 AlTPPCl was measured as 2.28(±0.02) ×107 dm6mol-2. In one case, the T1 crystal was obtained from Azo-py, binding to zinc tetraphenylporphyrinato. The Crystallography data of T1 and T3 were compared, indicating a conciderable deformation on zinc tetraphenylporphyrinato in T1 than T3. T1 and T3 tweezers, through exposure to mercury lamp, resulted in a dramatic color change in the solution from violet to green, due to the trans-cis isomerization which was compared with the corresponding color changes observed in this work. It seems that the shape ring deformation resulting from the trans-cis isomerization is effective in this color change. The result of the T1 reversibility test showed that T1 is reversible at 60 ° C. Further, the CVs of ZnTPP in the presence of various concentrations of Azo-py was examined, by which the Titration of ZnTPP by Azo-py causes displacement of oxidation peaks, which indicates on the formation of a complex between ZnTPP and Azo-py. The first redox wave of ZnTPP was progressively increased in the presence of T1 and T3, while the second oxidation wave moved to positive potentials. Moreover, the formation constant of T3 in cis isomer with C60 was calculated as 5.1(±0.2) ×109, using fluorescence method. The formation constant of T1 in trans and cis isomers with C60 was calculated as 1.2(±1.1) ×108 and 1.0(±0.3) ×108 dm6mol-2, respectively. The selectivity of the T3 was recorded towards different metal ions using fluorescence and absorption spectroscopy which indicated that T3 tweezers did not show selectivity for any metal ion. The interaction of T3 with amines and ammonium salts was also studied. The observed absorption spectra showed remarkable changes for the interaction of T3 with ammonium chloride. In other studies, the effect of different cations on the Azo-acid ligand was studied, the Azo-acid absorption spectrum was demonstrated noticeable changes, with increasing the concentration of the cations, indicating their interaction with linker ligand Azo-acid
  9. Keywords:
  10. Fullerene ; Molecular Tweezer ; Cyclic Voltammetry ; Cisplatin ; Tetraphenyl Porphyrin ; Azacrown Macrocycle with Pyridine Arms

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