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Synthetic Studies of Re(CO)3 Bioconjugates, Azadipyrromethenes, and Ferrocene-modified Compounds

Chanawanno, Kullapa
http://rave.ohiolink.edu/etdc/view?acc_num=akron1475756546217373

Abstract Details

2016, Doctor of Philosophy, University of Akron, Chemistry.
The rhenium tricarbonyl (Re(CO)3+) is one of the most commonly used organometallic cores for labeling various molecular types. The direct labeling of Re(I) via imine formation by the use of pyridine-2-carboxaldehyde (pyca) was achieved by coordination to the fac-[Re(CO)3]+. The Re(CO)3-aldehyde adduct reacts with a variety of aromatic/aliphatic amines and peptides resulting in Re(CO)3-conjugates. In the second chapter, this thesis presents a study on Re(CO)3 pyridine–imine complexes with pendant phenol groups. The effects of the position of the hydroxyl group (para, meta or ortho to the imine) were investigated. These compounds exhibit pH-dependent metal-to-ligand charge transfer bands. A series of Re(CO)3-imine with ferrocenyl units was presented in the third chapter. Hydrazine can be used as a linker to connect ferrocene and Re(CO)3, resulting in 1:1, 2:1, and 1:2 ferrocene:Re(CO)3 complexes. The electrochemistry and spectroscopy of the compounds were investigated and DFT and TDDFT calculations provided insight electronic structures of the conjugates. In the fourth chapter, this thesis presents a Re(CO)3-modified lysine that can be generated in a one-pot reaction. This Re(CO)3-modified lysine can be incorporated into four different peptides using solid phase peptide synthesis. And cellular uptake was monitored via the use of a fluorescein modified variant. The number of studies of azadipyrromethenes (ADPM) and their BF2 complexes (aza-BODIPY) has been growing due to their long-wavelength absorptions and high emissions observed in these compounds. Additionally, the discovery of the related novel fluorophore, BOPHY, by Ziegler’s group in 2014 has also initiated numerous studies focusing on the development of these compounds. In the next chapter, this thesis presents a study of structures and photophysical of ADPMs and several aza-BODIPYs. Both ADPMs and aza-BODIPYs are fluorescent, and the aza-BODIPYs exhibit red shifted emissions relative to their ADPMs analogs. In the subsequent chapter, the synthesis and characterization of the first ADPM and aza-BODIPY complexes with ferrocene directly connected to the a-pyrrolic carbon is reported. The ferrocene units are electronically coupled to each other. DFT and TDDFT calculations are in agreement with the experimental data. In the last experimental chapter, the first organometallic BOPHY substituted with two ferrocene units is reported. The study revealed an unprecedented long-range metal-metal coupling between the ferrocene-centered oxidation waves.
Christopher Ziegler (Advisor)
Claire Tessier (Committee Member)
Sailaja Paruchuri (Committee Member)
Wiley Youngs (Committee Member)
Thein Kyu (Committee Member)
Chemistry

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Citations

  • Chanawanno, K. (2016). Synthetic Studies of Re(CO)3 Bioconjugates, Azadipyrromethenes, and Ferrocene-modified Compounds [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1475756546217373

    APA Style (7th edition)

  • Chanawanno, Kullapa. Synthetic Studies of Re(CO)3 Bioconjugates, Azadipyrromethenes, and Ferrocene-modified Compounds. 2016. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1475756546217373.

    MLA Style (8th edition)

  • Chanawanno, Kullapa. "Synthetic Studies of Re(CO)3 Bioconjugates, Azadipyrromethenes, and Ferrocene-modified Compounds." Doctoral dissertation, University of Akron, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1475756546217373

    Chicago Manual of Style (17th edition)

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This open access ETD is published by University of Akron and OhioLINK.