Lighting up Pnictogen-Based Polymers: A Comparison of Phosphorus and Bismuth

  • Author / Creator
    Parke, Sarah M.
  • The work described in this thesis outlines the development of fluorescent and phosphorescent emitters based on the Group 15 elements, bismuth and phosphorus.
    Work began with the synthesis of a series of bismuth-containing heterocycles, termed bismoles and benzobismoles, via the copper(I) chloride-mediated metallacycle transfer chemistry of zirconacyclopentadienes. TD-DFT computations indicated that participation of the bismuth orbitals in the excitation process is correlated with the observed phosphorescence. This requirement gives rise to a method to predetermine if a system is likely to be phosphorescent, enabling TD-DFT to serve as a guide to direct development of new phosphorescent materials in the future.
    Norbornene-functionallized benzobismoles could be polymerized via ring-opening metathesis polymerization to produce weakly red phosphorescent products of high molecular weight. The use of Grubbs’ third generation catalyst enabled the formation of a benzobismole-based block copolymer that readily undergoes self-assembly into spherical micelles in THF/hexanes mixtures.
    This method of ring-opening metathesis polymerization of could be extended to a highly emissive benzophosphole oxide AIEgen-based monomer to yield fluorescent polymers. While this benzophosphole oxide monomer displayed drastically decreased quantum yield in solution compared to in the solid state, after polymerization the resulting solution state fluorescence quantum yield of the polymer increased to 30 %. Self-assembly of two different benzophosphole oxide block copolymers was achieved and the luminescence of these materials is reported.

  • Subjects / Keywords
  • Graduation date
    Fall 2019
  • Type of Item
  • Degree
    Doctor of Philosophy
  • DOI
  • License
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