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Development of Conjugated Organophosphorus Materials

Wang, Kai
http://orcid.org/0000-0003-4569-0909
http://rave.ohiolink.edu/etdc/view?acc_num=case1614616540043553

Abstract Details

2021, Doctor of Philosophy, Case Western Reserve University, Chemistry.
The development of materials featuring organic -conjugated systems continues to grow due to their potential and practical applications in optoelectronics. The incorporation of heteroatoms into the conjugated systems introduces new properties and additional tunability. In order to take advantage of the similarities between phosphorus and carbon, organic low valent phosphorus heterocycles, specifically 2-R-1,3-benzoxaphospholes (2-R-1,3-BOP) and 2-R-1,3-benzazaphospholes (2-R-1,3-BAP), are studied to understand their capacity to extended conjugation as well as to further explore their interesting luminescent properties. To achieve polymerization for a series of previously developed 2-R-1,3-BOPs, palladium catalyzed Suzuki-Miyaura reactions were examined in hopes of producing carbon-carbon bonded biaryl species that could participate in further cross coupling. The desired reactions did not proceed to give the expected compound, however, and instead led to the formation of an unidentified product. Chapter two of this work details the findings of the study and additional reactions carried out to identity the unknown product, which was later revealed to be an oxidized form of the 2-R-1,3-BOP by addition of a base across the P=C unit. In a related study, electropolymerization was probed to determine the feasibility of an alternative route to obtaining conjugated phosphorus materials. Bithiophene substituted 2-R-1,3-BAP was discovered to produce a blue film on the working electrode surface over repeated cyclic voltammetry experiments. This work is discussed in Chapter three, and investigates the possible route through which the electropolymerization occurs and examines the possible sites on the monomer unit through which the polymer formed. Taking advantage of the possibility of electropolymerization, a symmetric doubly substituted benzazaphosphole synthesis was proposed and analyzed. With the recent reports on the luminescent characteristics of 2-R-1,3-BAPs, it was of interest to probe further the interactions of variously substituted 2-R-1,3-BAPs with two types of divalent carbenes. Studies confirm the formation of two deprotonated benzazaphospholide salts; the fluorophores were found to display emission quenching when reacted with both carbenes at high concentrations and were found to have returned luminescence at low concentrations. The solid-state findings are discussed in Chapter four alongside solution-state NMR and photophysical characterization detailing the reversible nature of these benzazaphospholide salts.
John Protasiewicz (Advisor)
Irene Lee (Committee Chair)
Anthony Pearson (Committee Member)
David Schiraldi (Committee Member)
256 p.
Chemistry
synthesis; synthetic organometallic chemistry; chemistry; Phosphorus chemistry; Suzuki-Miyaura cross coupling; electropolymerization; 1,3-benzoxaphospholes; 1,3-benzazaphospholes

Recommended Citations

Citations

  • Wang, K. (2021). Development of Conjugated Organophosphorus Materials [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1614616540043553

    APA Style (7th edition)

  • Wang, Kai. Development of Conjugated Organophosphorus Materials. 2021. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1614616540043553.

    MLA Style (8th edition)

  • Wang, Kai. "Development of Conjugated Organophosphorus Materials." Doctoral dissertation, Case Western Reserve University, 2021. http://rave.ohiolink.edu/etdc/view?acc_num=case1614616540043553

    Chicago Manual of Style (17th edition)

case1614616540043553
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This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.