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61.
62.
Dications of cycloparaphenyles ([n]CPPs) are known to exhibit in-plane global aromaticity, contained in a nanobelt structure. Recently synthesized ortho and meta isomers of [n]CPPs break the radial symmetry of π structure incorporating perpendicular oriented π orbitals. Herein we set to explore the aromaticity of neutral and dicationic ortho and meta isomers of [8]CPP by dissecting the induced magnetic field to contributions of the twofold radial/perpendicular π system using delocalized canonical molecular orbitals (CMO), and introducing the natural localized molecular orbitals (NLMO) analysis with DFT methods. The dications sustain a reduced global aromatic character of the radial π system under a perpendicular orientation of the external field which declines from ortho to meta isomer and reinforces local aromaticity of ortho ring while it destroys aromaticity of meta ring. Aromaticity variations are determined by symmetry governed rotational excitations of frontier π orbitals. The parallel orientation reveals a substantial reduction of local aromaticity verified with NICSπ analysis and electron delocalization indices. 相似文献
63.
Iodice M Cusanno F Acha A Ambrozewicz P Aniol KA Baturin P Bertin PY Benaoum H Blomqvist KI Boeglin WU Breuer H Brindza P Bydzovský P Camsonne A Chang CC Chen JP Choi S Chudakov EA Cisbani E Colilli S Coman L Craver BJ De Cataldo G de Jager CW De Leo R Deur AP Ferdi C Feuerbach RJ Folts E Fratoni R Frullani S Garibaldi F Gayou O Giulani F Gomez J Gricia M Hansen JO Hayes D Higinbotham DW Holmstrom TK Hyde CE Ibrahim HF Jiang X Kaufman LJ Kino K Kross B Lagamba L LeRose JJ Lindgren RA 《Physical review letters》2007,99(5):052501
An experiment measuring electroproduction of hypernuclei has been performed in hall A at Jefferson Lab on a 12C target. In order to increase counting rates and provide unambiguous kaon identification two superconducting septum magnets and a ring imaging Cherenkov detector were added to the hall A standard equipment. An unprecedented energy resolution of less than 700 keV FWHM has been achieved. Thus, the observed (Lambda)(12)B spectrum shows for the first time identifiable strength in the core-excited region between the ground-state s-wave Lambda peak and the 11 MeV p-wave Lambda peak. 相似文献
64.
Tvaskis V Christy ME Arrington J Asaturyan R Baker OK Blok HP Bosted P Boswell M Bruell A Cochran A Cole L Crowder J Dunne J Ent R Fenker HC Filippone BW Garrow K Gasparian A Gomez J Jackson HE Keppel CE Kinney E Lapikás L Liang Y Lorenzon W Lung A Mack DJ Martin JW McIlhany K Meekins D Milner RG Mitchell JH Mkrtchyan H Moreland B Nazaryan V Niculescu I Opper A Piercey RB Potterveld DH Rose B Sato Y Seo W Smith G Spurlock K van der Steenhoven G Stepanyan S Tadevosian V Uzzle A Vulcan WF Wood SA 《Physical review letters》2007,98(14):142301
We report on a study of the longitudinal to transverse cross section ratio, R=sigmaL/sigmaT, at low values of x and Q2, as determined from inclusive inelastic electron-hydrogen and electron-deuterium scattering data from Jefferson Laboratory Hall C spanning the four-momentum transfer range 0.06相似文献
65.
66.
We present specific heat data on three samples of the dilute Ising magnet LiHoxY1-xF4 with x=0.018, 0.045, and 0.080. Previous measurements of the ac susceptibility of an x=0.045 sample showed the Ho3+ moments to remain dynamic down to very low temperatures, and the specific heat was found to have unusually sharp features. In contrast, our measurements do not exhibit these sharp features in the specific heat and instead show a broad feature, for all three samples studied, which is qualitatively consistent with a spin glass state. Integrating C/T, however, reveals an increase in residual entropy with lower Ho concentration, consistent with recent Monte Carlo simulations showing a lack of spin glass transition for low x. 相似文献
67.
Access to Optically Active 3‐Substituted Piperidines by Ring Expansion of Prolinols and Derivatives
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Dr. Domingo Gomez Pardo Prof. Janine Cossy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4516-4525
The ring expansion of prolinols via an aziridinium intermediate gives C3‐substituted piperidines in good yields and enantiomeric excess, the substituent at the C3 position being derived from the most reactive nucleophile in the reaction mixture. Depending on the nucleophile, the reaction proceeds under thermodynamic or kinetic control. The regioselectivity of attack of nucleophiles on the aziridinium intermediate depends on the nature of the substituents on the nitrogen atom and the C4 position of the starting prolinols. 相似文献
68.
Water‐Stable Zirconium‐Based Metal–Organic Framework Material with High‐Surface Area and Gas‐Storage Capacities
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Dr. Oleksii V. Gutov Dr. Wojciech Bury Dr. Diego A. Gomez‐Gualdron Dr. Vaiva Krungleviciute Dr. David Fairen‐Jimenez Dr. Joseph E. Mondloch Dr. Amy A. Sarjeant Salih S. Al‐Juaid Prof. Dr. Randall Q. Snurr Prof. Dr. Joseph T. Hupp Prof. Dr. Taner Yildirim Prof. Dr. Omar K. Farha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(39):12389-12393
We designed, synthesized, and characterized a new Zr‐based metal–organic framework material, NU‐1100 , with a pore volume of 1.53 ccg?1 and Brunauer–Emmett–Teller (BET) surface area of 4020 m2g?1; to our knowledge, currently the highest published for Zr‐based MOFs. CH4/CO2/H2 adsorption isotherms were obtained over a broad range of pressures and temperatures and are in excellent agreement with the computational predictions. The total hydrogen adsorption at 65 bar and 77 K is 0.092 g g?1, which corresponds to 43 g L?1. The volumetric and gravimetric methane‐storage capacities at 65 bar and 298 K are approximately 180 vSTP/v and 0.27 g g?1, respectively. 相似文献
69.
Hong-Lei Xu Dr. Ivan A. Popov Nikolay V. Tkachenko Dr. Zi-Chuan Wang Prof. Dr. Alvaro Muñoz-Castro Prof. Dr. Alexander I. Boldyrev Prof. Dr. Zhong-Ming Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17439-17443
In this work, the largest heterometallic supertetrahedral clusters, [Zn6Ge16]4− and [Cd6Ge16]4−, were directly self-assembled through highly-charged [Ge4]4− units and transition metal cations, in which 3-center–2-electron σ bonding in Ge2Zn or Ge2Cd triangles plays a vital role in the stabilization of the whole structure. The cluster structures have an open framework with a large central cavity of diameter 4.6 Å for Zn and 5.0 Å for Cd, respectively. Time-dependent HRESI-MS spectra show that the larger clusters grow from smaller components with a single [Ge4]4− and ZnMes2 units. Calculations performed at the DFT level indicate a very large HOMO–LUMO energy gap in [M6Ge16]4− (2.22 eV), suggesting high kinetic stability that may offer opportunities in materials science. These observations offer a new strategy for the assembly of heterometallic clusters with high symmetry. 相似文献
70.
In the literature it was found that titanium oxide clusters of a few metal atoms encapsulated inside the micropores of zeolite Y exhibit large blue shifts in the Ti-O ligand-to-metal charge-transfer band as compared to non-encapsulated bulk titanium dioxide particles. This blue shift of the Ti-O absorption band is believed to have a negative effect on the photocatalytic activity of zeolite-encapsulated TiO2. We report here on circumventing this problem and increasing visible-light absorption by means of a red shift of the absorption band caused by addition of some organic molecular modifiers containing acidic OH groups that can strongly bind with titanol groups TiOH. In the studied series of zeolite-encapsulated TiO2 samples, the red shift of the optical spectrum follows the order: catechol > 4-aminobenzoic acid > benzoic acid. Also N-doping of zeolite-encapsulated TiO2 clusters by thermal treatment with urea leads to a red shift of the TiO2 absorption band that depends on the annealing and hydration conditions. By comparison to the degradation of phenol in aqueous solution, we have demonstrated that these changes in the absorption spectrum on addition of the organic modifier are also reflected in the photocatalytic activity of the samples; a greater increase in photocatalytic activity (about 30%) was observed for the additive catechol. 相似文献