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Synthesis and Supramolecular Chemistry of 2,4,9-Trithiaadamantane Derivatives

Khemtong, Chalermchai
http://rave.ohiolink.edu/etdc/view?acc_num=akron1123084162

Abstract Details

2005, Doctor of Philosophy, University of Akron, Chemistry.
This dissertation describes the synthesis and supramolecular chemistry of 7-substituted-2,4,9-trithiaadamantanes. The structurally well-defined molecular building block was prepared by a multi-step synthesis from dimethyl malonate or diethyl malonate. A new synthetic method for the formation of a 2,4,9-trithiaadamantane ring system was developed using the combination of Lawesson’s reagent and a Lewis acid. The method improved the reaction yields to 35-40%. The ethyl or methyl ester group attached to position 7 of the 2,4,9-trithiaadamantane ring was converted to other functionalities depending upon the applications. These functional groups include a carboxylic acid, an alcohol, an aldehyde, a long chain amide, and alkynes. Additionally, the introduction of a diazomethylcarbonyl group or an azidocarbonyl group produced the photolabile molecular surface anchors. 2,4,9-Trithiaadamantan-7-yl-ethyne facilitated the synthesis of molecular wires via the Sonogashira cross coupling reaction with various phenyl halides. 1,4-Bis((7-2,4,9-trithiaadamantyl)ethynyl) benzene, 1,4-bis(7-2,4,9-trithiaadamantyl) butadiyne, S-{4-[4-[7-2,4,9-trithiaadamantylethynyl]-phenylethynyl]-phenyl} thioacetate and 4-[4-[7-2,4,9-trithiaadamantylethynyl]-phenylethynyl]-pyridine, were prepared. 2,4,9-Trithiaadamantane-7-carboxylic acid octadecylamide (TPCONHC18) was used as a ligand for stabilizing gold nanoparticles. Ligand exchange reaction of triphenylphosphine-stabilized gold nanoparticles with TPCONHC18 produced tripodal ligand-stabilized gold nanoparticles of an average size of 88.2 ± 21.6 nm. Gold nanoparticles prepared by the Brust-Schiffrin method using a 1:1 ligand to gold ratio are about 86.3 ± 14.2 nm. The inclusion complex of 2,4,9-trithiaadamantane-7-carboxylic acid (TPCOOH) in β-cyclodextrin was studied by 1H NMR and 2D nuclear overhauser effect spectroscopy (NOESY), host induced circular dichroism spectroscopy (CD), and tandem mass spectrometry. The 1H NMR, MS-MS and the NOESY data show that the TPCOOH guest forms a 1:1 inclusion complex with the host β-cyclodextrin. The NOESY experiments also showed that TPCOOH is oriented in the complex with the thioketal end preferentially located at the larger opening of β-cyclodextrin. The orientation of the guest in the host molecule is also confirmed by the induced CD of the ligand which shows a positive Cotton effect. An association constant of 663 ± 20 M-1 was determined by 1H NMR titration for the complex at room temperature in D2O.
Jun Hu (Advisor)
152 p.
Chemistry, Organic
2; 4; 9-trithiaadamantane; cyclodextrin; gold nanoparticles; synthesis; molecular wires; surface anchor

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Citations

  • Khemtong, C. (2005). Synthesis and Supramolecular Chemistry of 2,4,9-Trithiaadamantane Derivatives [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1123084162

    APA Style (7th edition)

  • Khemtong, Chalermchai. Synthesis and Supramolecular Chemistry of 2,4,9-Trithiaadamantane Derivatives. 2005. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1123084162.

    MLA Style (8th edition)

  • Khemtong, Chalermchai. "Synthesis and Supramolecular Chemistry of 2,4,9-Trithiaadamantane Derivatives." Doctoral dissertation, University of Akron, 2005. http://rave.ohiolink.edu/etdc/view?acc_num=akron1123084162

    Chicago Manual of Style (17th edition)

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