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Design and Synthesis of the Late Transition Metal Complexes Based on Naphthalimide and Pyridine Ligands and Study of their Photophysical Properties

Hendi, Zohreh | 2022

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  1. Type of Document: Ph.D. Dissertation
  2. Language: Farsi
  3. Document No: 54836 (03)
  4. University: Sharif University of Technology
  5. Department: Chemistry
  6. Advisor(s): Jamali, Sirous
  7. Abstract:
  8. 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 the quantum yield efficiencies was observed along with increases in metal ionic radius, consistent with the increase in the intramolecular π-interactions between the two adjacent naphthalimide units and in the dihedral angle α. Surprisingly, the enhancement in quantum yield of amino-substituted derivative 6 in solution was unusually large that can be attributed to the adjacent naphthalimide units’ locking, resulting in restrictions in the intramolecular vibrational and rotational motions and its quenching in solid state may be due to the different mechanisms such as intermolecular energy transfer via Dexter mechanism.In the second project, we described the synthesis and characterization of the first platinum(IV) metal-organic cage [(Me3PtIV)8(byp)12](Otf)8, 2, a metal-organic cage using a third-row transition metal in a higher oxidation state in which the organometallic moieties trimethylplatinum(IV) occupied the corners of a cubane structure and 4,4’-bipyridine ligands used as linkers. This study shows that the tetrameric trimethylplatinum(IV) compound [Me3Pt(Otf)]4, 1, is suitable precursor for the synthesis of platinum(IV)-organic cages. The first-principle density functional theory (DFT) calculations showed that HOMOs orbitals were localized on the PtMe3 moieties, while the LUMOs orbitals were distributed on the organic linkers
  9. Keywords:
  10. Complexes ; Ligands ; Emission Properties ; Reactivity ; Metal-Organic Cages ; 1,8-Naphthyridine ; Bidentate Pyridine Ligands

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