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Title: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. University of Iowa Department of Chemistry, 52242 Iowa City IA USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400825
Grant/Contract Number:
SC0013980
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Volume: 2017; Journal Issue: 13; Related Information: CHORUS Timestamp: 2017-10-20 15:50:59; Journal ID: ISSN 1434-1948
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

de Groot, Joshua, Cassell, Brittany, Basile, Madeline, Fetrow, Taylor, and Forbes, Tori Z. Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds. Germany: N. p., 2017. Web. doi:10.1002/ejic.201700024.
de Groot, Joshua, Cassell, Brittany, Basile, Madeline, Fetrow, Taylor, & Forbes, Tori Z. Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds. Germany. doi:10.1002/ejic.201700024.
de Groot, Joshua, Cassell, Brittany, Basile, Madeline, Fetrow, Taylor, and Forbes, Tori Z. Tue . "Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds". Germany. doi:10.1002/ejic.201700024.
@article{osti_1400825,
title = {Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds: Charge-Assisted Hydrogen-Bonding and Crystallization Effects within U VI Glycine Compounds},
author = {de Groot, Joshua and Cassell, Brittany and Basile, Madeline and Fetrow, Taylor and Forbes, Tori Z.},
abstractNote = {},
doi = {10.1002/ejic.201700024},
journal = {European Journal of Inorganic Chemistry},
number = 13,
volume = 2017,
place = {Germany},
year = {Tue Apr 04 00:00:00 EDT 2017},
month = {Tue Apr 04 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/ejic.201700024

Citation Metrics:
Cited by: 2works
Citation information provided by
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  • A photoelectron spectrum is reported for an anionic complex of uracil (U) with HCN. The effects of electron attachment to a complex of U with HA (A = CN, NC) have been studied at the density functional theory level with 6-31++G** basis sets and the B3LYP and MPW1K exchange correlation functionals. Critical anionic structures have been reexamined at the MP2/6-31++G** level. The B3LYP gas phase deprotonation enthalpies are equal to 14.56, 15.13, and 15.12 eV for HNC, HCN, and H{sub 2}S, respectively. The experimental deprotonation enthalpies are 15.100 {+-} 0.008 and 15.214 {+-}0.125 eV for HCN and H{sub 2}S, respectively.more » Hence, HCN and H{sub 2}S have very similar deprotonation enthalpies. The photoelectron spectra of anionic complexes of uracil with HCN and H{sub 2}S are, however, very different. The (UHCN){sup -} spectrum reveals a broad feature with a maximum between 1.2-1.4 eV, whereas the main feature of the (UH{sub 2}S){sup -} spectrum has a maximum between 1.7 and 2.1 eV. We suggest that barrier-free proton transfer (BFPT) [Eur. Phys. J. D 2002, 20, 431-439; J. Phys. Chem. B 2003, 107, 7889-7895] occurs in the (UH{sub 2}S){sup -} complex but not in (UHCN){sup -}. Critical factors for the occurrence of BFPT have been analyzed. The difference between the (UHCN){sup -} and (UH{sub 2}S){sup -} complexes is attributed to differences in hydrogen bonds formed by HCN and H{sub 2}S with uracil.« less
  • Radicals R. derived from azo compounds abstract hydrogen atoms from thiophenol giving RH, and the tritium effect is readily measured by comparing the activity of C/sub 6/H/sub 5/SH* and RH*. Azo compounds of the form (CH/sub 3/)/sub 2/CXN=NCX(CH/sub 3/)/sub 2/ also yield RH by a disproportionation; in these cases k/sub D//k/sub T/ was measured after correction for contamination of RD* by RH. In these examples, covering X=C/sub 6/H/sub 5/S, CH/sub 3/OC(=0), N triple bond C, and C/sub 6/H/sub 5/, there was good correlation between k/sub D//k/sub T/ and k/sub H/ (measured by others); both are related to the stability ofmore » the radical R. The isotope effects are rather small. Aryl radicals, from Ar.N=NC(C/sub 6/H/sub 5/)/sub 3/, were also studied. The values are quite small (k/sub H//k/sub T/ = 1.4 to 3.1). Evidence is presented to support an important contribution of polar structures to the transition state. The basis of the influence of these transition state polar contributions on the isotope effect is considered; the same considerations also explain the steric enhancement of isotope effects. (auth)« less
  • No abstract prepared.
  • The optical nonlinear effects that result from electrooptic index perturbations which are induced by space-charge fields that result from photocharge separation respond to low intensity levels. The photorefractive two-beam coupling, absorption and photoluminescence spectroscopy measurements in vanadium-doped cadmium-telluride reveals that photorefractive carriers are electrons that are excited from vanadium's V[sup 2+] ground level at 0.78 eV below the conduction-band. Measurements at 1.5 [mu]m wavelength confirm the theoretically expected high photorefractive sensitivity of CdTe. Application of nominally square ac field enhances the beam-coupling gain coefficient at 1.3 [mu]m to values at high as 10 cm[sup [minus]1]. The gain coefficient is influencedmore » by pulse shape, beam ratio and field-screening. Optimum ac period needs to be shorter than the dielectric-relaxation time which is orders of magnitude shorter than the dielectric-relaxation time which is orders of magnitude shorter that the photorefractive response time. The author has observed two-wave mixing in vanadium-doped zinc-telluride at wavelengths from 0.6 to 1.3 [mu]m. Photorefractive effect in cadmium-zinc-telluride ternary alloy with 4% and 10% zinc content was also determined. The author studied the interelectrode electric field distribution in indium-doped CdTe. Below bandgap extrinsicly absorbed light light results in accumulation of the applied voltage across a narrow region under the negative electrode. The resulting high electric fields which have a charge-transport origin are used in various optical switching devices. The field-screening effect in CdTe:In is a versatile nonlinearity which the author has used for optical-limiting and various forms of optical neuron devices.« less
  • It was previously shown that the addition of 1 equiv of a strong acid to [Mn{sup IV}(salpn)({micro}-O)]{sub 2}, 1, generates the oxo/hydroxo complex [{l{underscore}brace}Mn{sup IV}(salpn){r{underscore}brace}{sub 2}({micro}-O,{micro}-OH)](CF{sub 3}SO{sub 3}), 2, which emphasized the basicity of the {micro}{sub 2}-O{sup 2{minus}} units in the [Mn{sup IV}({micro}-O)]{sub 2} dimers. The authors now demonstrate the inherent nucleophilicity of those {micro}{sub 2}-O{sup 2{minus}} units by showing that the addition of methyl triflate to 1 results in formation of the oxo/methoxo-bridged Mn{sup IV} dimer [{l{underscore}brace}Mn{sup IV}(salph){r{underscore}brace}{sub 2}({micro}-O,{micro}-OCH{sub 3})](CF{sub 3}SO{sub 3}), 3. EXAFS analysis of 3 demonstrates that alkylation of an oxo bridge results in the same structuralmore » modification of the [Mn{sup IV}({micro}-O)]{sub 2} core as an oxo bridge protonation. Electrochemical and spectroscopic comparisons of 3 to 2 indicate that 3 is a good electronic structure analogue for 2 without the complication of proton lability and hydrogen bonding. Indeed, 2 and 3 react nearly identically with hydrogen peroxide and with strong acids. In contrast, the products of their reactions with amines, acetate, and triphenylphosphine are dramatically different. The proton lability of 2 results in simple proton transfer, circumventing the slower redox reactions of these substrates with 3. Isotopic labeling, kinetic, and EPR-monitored radical trap studies lead to a proposed reduction-oxidation mechanistic scheme for the reactions of 3 with amines and triphenylphosphine. The Mn{sup III} product of this reaction, [Mn{sup III}(salpn)(Ph{sub 3}PO)](CF{sub 3}SO{sub 3}), was isolated and crystallographically characterized as a dimerized complex. The redox nature of the reactions is confirmed by trapping of a reduced Mn intermediate which is identified by EPR spectroscopy. Comparison of the reactions of 2 and 3 demonstrates the dramatic effect of proton lability and hydrogen bonding on reactivity, and suggests how metalloenzymes may regulate active site reactivity to produce very different catalytic activity with similar active site structures. Furthermore, it also emphasizes that caution should b4e used when the reactivity of model compounds with easily and rapidly dissociable protons is assessed.« less