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published_or_final_version / Physics / Doctoral / Doctor of Philosophy

Bibliography: leaves 143-153. Studies the complexation of metal ions with the macrocyclic ligand, 1, 4, 8, 11-tetrakis (2-hydroxyethyl)-1, 4, 8, 11-tetraazacyclotetradecane (THEC)

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The purpose of this research was to synthesize a novel crown ether compound that has been designed to fluoresce with greatly enhanced intensities when in the presence of selected alkali metal cations. The novel crown ether compound (cryptand) 12,25-(1,5 - dimethyloxynaphtho)-1,4,7,10,14,17,20,23-octaoxacyclohexacosane (1) was synthesized through 6 steps. The general synthetic route for the preparation of cryptand 1 is given in the proposed synthetic procedure. Reaction of benzaldehyde (23) with glycerol (24) in the presence of concentrated sulfuric acid afforded cis and traps-1,3-O-benzylideneglycerol (25). Cis and trans-2-O-benzyl-1,3-O-benzylideneglycerol (27) was obtained when 1,3O-benzylideneglycerol (25) was treated with benzyl bromide (26) and sodium wire in benzene. Acid-hydrolysis of the 2-O-benzyl-1,3-O-benzylideneglycerol (27) in methanol gave 2-O-benzylglcerol (28). The key starting material is 12,25-bisbenzyloxy1,4,7,10,14,17,20,23-octaoxacyclohexacosane (31), which requires the formation of four carbon-oxygen bonds. 2-O-benzylglcerol (28) was reacted with triethyene glycol ditosylate and sodium hydride in dioxane. This treatment gave the product 12,25-bisbenzyloxy1,4,7,10,14,17,20,23-octaoxacyclohexacosane likely to be (31) along with the 1:1 and a 3:3 crown ether products. The compound likely to be (31) was treated with H2 and a Pd/Ccatalyst and the resulting compound was 12,25-dihydroxy-1,4,7,10,14,17,20,23Octaoxacyclohexacosane (2). Compound likely to be (2) was reacted with 1,5bis(bromomethy)naphthalene and potassium t-butoxide in tetrahydrofuran to give the final cryptand compound 1. The structures of the crown ethers, the products of this reaction, have not yet been unambiguously assigned. / Department of Chemistry

Reprints of five arricles by the author bound in at back of volume / iv, 201 leaves : ill. ; 27 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1974

This dissertation is concerned with the first experimental observation of the vibration-rotation spectrum of the helium molecular ion, ³He⁴He⁺. The Doppler-tuned fast-beam laser-resonance technique has been used. The ions produced in an electron-impact ion source form an ion beam of a few KeV and then intersect nearly colinearly with a CO IR laser beam of fixed frequency. The velocity of the ions is scanned to tune the ions into resonance with the laser frequency. Subsequent resonance detection is realized by using charge exchange processes of the ion with a target gas. Twelve spectral lines have been measured which correspond to nine different vibration-rotation transitions of the R branch in the fundamental band of the ground state of ³He⁴He⁺. The combination of the kinematic compression of the fast-beam method and the special frequency stabilization of the CO laser render an experimental accuracy of 0.0006 cm⁻¹ or 0.4 ppm. The accuracy exceeds that of the available theory by three orders of magnitude. The narrow spectral linewidth also allows partial resolution of the magnetic hyperfine structure due to helium-3. A hyperfine structure calculation has been carried out using a numerical multi-configuration self-consistent-field method. The agreement between the calculation and the observation is very satisfying.

The infrared vibrational-rotational spectra of the deuterated triatomic hydrogen molecular ions, H₂D⁺, HD₂⁺, and D₃⁺ have been observed with the Doppler-tuned ion-beam laser spectroscopic method with collision detection. Triatomic hydrogen molecular ions are produced in a coaxial electron-impact ion source. Next, the ions are accelerated and formed into a beam of several keV energy, which is then intercepted at a small angle by a frequency-stabilized CO laser beam. The energy of the ion beam is adjusted to Doppler-shift an ion transition into resonance with a nearby laser line. On resonance, the laser light stimulates the transition to take place. If the resonating states differ in population, the laser-induced transition produces a net population transfer. The occurrence of population transfer is detected by monitoring the transmission of the ion beam through a gas target after laser interaction. The transmission through the target is dependent upon the ion beam population distribution and, therefore, the laser-induced transition can be detected by detecting the change of the transmission of the ion beam. A mass analyzer before the target gas facilitates the mass identification of the observed transitions. We have measured 45 D₃⁺ transition frequencies, 9 H₂D⁺ transition frequencies, and 31 HD₂⁺ transition frequencies, all between 1650 and 2000 cm⁻¹, to better than ±0.0005 cm⁻¹ or ±0.3 ppm. The identifications of the quantum numbers are still in progress. This study should greatly help the search of H₃⁺ and H₂D⁺ ions in interstellar medium.

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published_or_final_version / Physics / Doctoral / Doctor of Philosophy