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Synthesis and Characterization of Luminescent Gold(III) Complexes

Sulicz, Amanda N
http://rave.ohiolink.edu/etdc/view?acc_num=case1499423790277079

Abstract Details

2017, Doctor of Philosophy, Case Western Reserve University, Chemistry.
The chemistry of cyclometalated gold(III) has been relatively slow to emerge, but recent advances in catalyst and material design have driven a renewed interest. Reported here are synthetic, structural, and optical studies of cyclometalated gold(III) aryl complexes. These new complexes show ligand-centered luminescence that is perturbed by the heavy-atom effect of gold. Traditionally, metal-carbon bond formation relied on organometallic complexes of electropositive elements, including lithium and magnesium. The easily reducible nature of gold(III) often interferes with these conventional reagents, thus resulting in the use of toxic metals like mercury or thallium. Reported here is the use of palladium-catalyzed Suzuki-Miyaura cross-coupling for the attachment of aryl ligands to cyclometalated gold(III) chloride complexes. The resulting di- and mono-arylated species were luminescent. Several complexes have been crystallographically characterized. Luminescent derivatives of a previously published gold(III) chloro precursor, initially reported for catalytic purposes, were prepared through boron transmetalation reactions. Complexes bearing both aryl and cyanide ligands were synthesized. These luminescent materials are diamagnetic and were be characterized by multinuclear NMR, absorption and emission spectroscopies (including time-resolved emission), and by X-ray diffraction crystallography. The synthesized gold(I) complexes were designed to display reverse saturable absorption and be a two photon acceptor. The BTF (BTF = 2-(9,9’-diethyl-9H-fluoren-2-yl)-benzothiazole) ligand was chosen as it has been previously demonstrated to have favorable photophysical effects on platinum(II) and ruthenium(II) complexes for applications in photodynamic therapy and optical power limiting (OPL). Gold(I) complexes with the BTF ligand are sought for potential OPL applications. Synthesized complexes are luminescent and were characterized by multinuclear NMR, absorption and emission spectroscopies, photoluminescent quantum yields, time-resolved emission. Two complexes were crystallographically characterized.
Thomas Gray (Advisor)
Anthony Pearson (Committee Chair)
John Protasiewicz (Committee Member)
Rajesh Viswanathan (Committee Member)
Horst von Recum (Committee Member)
264 p.
Chemistry; Inorganic Chemistry

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Citations

  • Sulicz, A. N. (2017). Synthesis and Characterization of Luminescent Gold(III) Complexes [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1499423790277079

    APA Style (7th edition)

  • Sulicz, Amanda. Synthesis and Characterization of Luminescent Gold(III) Complexes. 2017. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1499423790277079.

    MLA Style (8th edition)

  • Sulicz, Amanda. "Synthesis and Characterization of Luminescent Gold(III) Complexes." Doctoral dissertation, Case Western Reserve University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=case1499423790277079

    Chicago Manual of Style (17th edition)

case1499423790277079
219
© 2017, some rights reserved.Creative Commons License Synthesis and Characterization of Luminescent Gold(III) Complexes by Amanda N Sulicz is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. Based on a work at etd.ohiolink.edu.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.