4 resultados para 9-ARYLCARBAZOLE MOIETIES
em CaltechTHESIS
Resumo:
Zintl phases, a subset of intermetallic compounds characterized by covalently-bonded "sub-structures," surrounded by highly electropositive cations, exhibit precisely the characteristics desired for thermoelectric applications. The requirement that Zintl compounds satisfy the valence of anions through the formation of covalent substructures leads to many unique, complex crystal structures. Such complexity often leads to exceptionally low lattice thermal conductivity due to the containment of heat in low velocity optical modes in the phonon dispersion. To date, excellent thermoelectric properties have been demonstrated in several Zintl compounds. However, compared with the large number of known Zintl phases, very few have been investigated as thermoelectric materials.
From this pool of uninvestigated compounds, we selected a class of Zintl antimonides that share a common structural motif: anionic moieties resembling infinite chains of linked MSb4 tetrahedra, where $M$ is a triel element. The compounds discussed in this thesis (
Resumo:
The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH3CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)2vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir LIII edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.
Resumo:
Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.
Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.
Resumo:
The reaction 7Li(3He, p)9Be has been used to measure excitations and intrinsic widths of levels in 9Be below the 7Li + d threshold. Previously unreported levels have been found at excitations of (13.78 ± .03) MeV and (16.671 ± .008) MeV with widths of (590 ± 60) keV and (41 ± 4) keV respectively. Two overlapping levels have been found at (11.81 ± .02) MeV and (11.29 ± .03) MeV with widths of (400 ± 30) keV and (620 ± 70) keV respectively. Branching ratios from 9Be levels populated in this reaction to the ground and first excited states of 8Be have been measured by observing the associated protons in coincidence with the decay neutrons. Branching ratios were found to be:
Excitation in 9Be .... Branching Ratio.......... Final Nucleus.........
(MeV) .......................... (percent) .....................................
.. 2.43 ........................... 7.5 ± 1.5 .............. 8Be(g.s.)
.. 3.03 ........................... 87 ± 13......................................
.. 4.65 ........................... 13 ± 4.......................................
.. 6.76 .............................. ≤ 2 ......................................
.. 11.29 ...............................≤ 2 ......................................
.. 11.81 ...............................≤ 3 ......................................
.. 6.76 ........................... .41 ≤ B.R. ≤ .69 ....... 8Be(2+)
.. 11.29 ........................... 14 ± 4 .......................................
.. 11.81 ........................... 12 ± 4 .......................................
Corresponding reduced widths for neutron emission are calculated and a comparison of the results with the expectations of current nuclear models is made. In particular the measured branching ratio to 8Be(g.s.) from 9Be(2.43 MeV) corresponds to an f-wave reduced with θ2f = 2.1 x 10-2, in units of ħ2/mR2, with R = 4.35 fm. A comparison of this value with that predicted by a Nilsson model calculation, in which 9Be is taken to be a deformed nucleus, is discussed. The measured value for θ2f is found to be consistent with that expected on the basis of measured E2-transition rates between rotational levels in 9Be.