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21.
Muranaka A Matsumoto Y Uchiyama M Jiang J Bian Y Ceulemans A Kobayashi N 《Inorganic chemistry》2005,44(11):3818-3826
A series of heteroleptic rare-earth sandwich complexes [M(Nc)(OEP)] (M = La, Nd, Eu, Dy, and Lu; Nc = 2,3-naphthalocyaninate; OEP = octaethylporphyrinate) have been investigated by electronic absorption and magnetic circular dichroism (MCD) spectroscopy. The electronic absorption spectra of the neutral forms showed two characteristic transitions (bands I and II) in the near-IR region, both of which were systematically shifted depending on the size of their central metal. In the MCD spectra, a relatively intense Faraday A term and a significantly weak Faraday B term have been observed corresponding to bands II and I, respectively. The spectral features were successfully interpreted using a simple MO model by considering the relevant interactions of Gouterman's four orbitals of the constituent chromophores. The model succeeded in assigning the MCD spectra of the related compounds, the oxidized and reduced forms of the dimer ([M(Nc)(OEP)]+ and [M(Nc)(OEP)]-), and neutral forms of the triple-decker compounds (M2(Nc)(OEP)2, M = Nd, Eu). DFT calculations of the dimers supported the validity of this model. 相似文献
22.
Xiaoqing Zeng Maofa Ge Zheng Sun Jiang Bian Dianxun Wang 《Journal of Molecular Structure》2007,840(1-3):59-65
Gaseous nitryl azide N4O2 is generated by the heterogeneous reaction of gaseous ClNO2 with freshly prepared AgN3 at −50 °C. The geometric and electronic structure of the molecule in the gas phase has been characterized by in situ photoelectron spectroscopy (PES) and quantum chemical calculations. The experimental first vertical ionization energy of N4O2 is 11.39 eV, corresponding to the ionization of an electron on the highest occupied molecular orbital (HOMO) {4a″(πnb(N4–N5–N6))}−1. An apparent vibrational spacing of 1600 ± 60 cm−1 (νasO1N2O3) on the second band at 12.52 eV (πnb(O1–N2–O3)) further confirms the preference of energetically stable chain structure in the gas phase. To complement the experimental results, the potential-energy surface of this structurally novel transient molecule is discussed. Both calculations and spectroscopic results suggest that the molecule adopts a trans-planar chain structure, and a five-membered ring decomposition pathway is more favorable. 相似文献
23.
Zhida Chen Yuqing Deng Jiang Bian Lemin Li Guangxian Xu 《Journal of Molecular Structure》1998,434(1-3)
A nonlocal density functional theory (DFT) method has been applied to the calculations on optimized geometry, Mulliken atomic net charges and interatomic Mulliken bond orders as well as total bonding energies (E) in the binary transition metal carbonyl anions with different reduced states [M(CO)n]z− (M=Cr, n=5, 4, 3, z=2, 4, 6; M=Mn, n=5, 4, 3, z=1, 3, 5; M=Fe, n=4, 3, 2, z=2, 4, 6; M=Co, n=4, 3, 2, z=1, 3, 5). For comparison of relative stability, a relative stabilization energy D is defined as D=E([M(CO)n]z−)−nE(CO). The calculated C–O distances are lengthened monotonously with the increase of the anionic charge, but the M–C distances are significantly lengthened only in the higher reduced states. The relative stabilization energy calculated is a considerable negative value in the lower reduced states, but a larger positive value in the higher reduced states. The DFT calculations show that with the increase of the anionic charge, the Mulliken net charges on the M, C, and O atoms all increase, however, an excess of the anionic charge is mainly located at the central metal atom. The calculated C–O Mulliken bond orders decrease consistently with the increase of the anionic charge, but the M–C bond orders exhibit an irregular behavior. However, the total bond orders calculated clearly explain the higher reduced states to be considerably unstable. From analysis of the calculated results, it is deduced that the stability of the binary transition metal carbonyl anions [M(CO)n]z− studied are associated with the coordination number n and the anionic charge z, further, it is possible for the anions studied to be stable if n≥z, conversely, it is impossible when n<z. 相似文献
24.
溴酸钾氧化亮绿SF催化光度法测定痕量亚硝酸根 总被引:27,自引:3,他引:27
本文基于亚硝酸根对溴酸钾氧化亮绿SF而使其褪色所起的催化作用,建立了高灵敏度催化吸光光度法测定痕量亚硝酸根的新方法,测定范围为0.05-20ng/ml,用于不同水样中亚硝酸根的测定,获得了满意结果。 相似文献
25.
聚N,N-二乙基丙烯酰胺溶液粘度的温度依赖性 总被引:2,自引:0,他引:2
通过自由基聚合,合成了线型聚N,N-二乙基丙烯酰胺(PDEA),用乌氏粘度计测定并考察了该聚合物在四氢呋喃(THF)、H2O以及THF-H2O混合溶剂中粘度的温度依赖性.实验结果表明,PDEA 在上述三种溶剂中粘度的温度依赖性不同,PDEA-THF体系的相对粘度随温度升高而增大;PDEA-H2O体系以及PDEA-THF-H2O体系的相对粘度随温度升高而减小,且THF体积分数φTHF < 0.7时具有透明-白浊转变现象;对PDEA-THF-H2O体系,φTHF增加,透明-白浊转变温度升高,而当φTHF=0.7时,则观察不到透明-白浊转变现象. 相似文献
26.
Bian Y Wang R Jiang J Lee CH Wang J Ng DK 《Chemical communications (Cambridge, England)》2003,(10):1194-1195
Treatment of MIII(Pc)(acac) (M = Sm, Eu, Gd; Pc = phthalocyaninate; acac = acetylacetonate), generated in situ, with 3-(3-pentyloxy)phthalonitrile in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol affords racemic mixtures of the chiral double-deckers MIII(Pc)[Pc(OC5H11)4] [Pc(OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninate], which have been spectroscopically and structurally characterised. 相似文献
27.
Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape 总被引:3,自引:0,他引:3
Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding. 相似文献
28.
Li-an Bian Peiguo Liu Qihui Zhou Chenxi Liu Hanqing Liu Song Zha 《Optical and Quantum Electronics》2018,50(5):220
Total absorption is realized theoretically in a graphene-outside-cavity resonator. The structure is composed of the FP-Fano hybrid resonance cavity. Changing the thickness of grating exciting Fano resonance, the absorption-mode number can be tuned effectively. For the focused double-mode absorption, the resonances behave insensitively with the variation of chemical potential of graphene. Varying the geometry of grating can control the coupling extent of two modes. Also, by manipulating the period number of two-side multilayers around graphene, the absorption, shift and number of modes are governed. 相似文献
29.
Wang Kang Xingqiong Du Lanzhi Wang Lijuan HU Yuhuan Dong Yanqing Bian Yuan Li 《中国化学》2013,31(10):1305-1314
Our studies examined the structural features responsible for the antifungal activity of 2-ethoxycarbonyl-1,5- benzothiazepine (7a). Three series of 1,5-benzothiazepine derivatives were synthesized and screened for their antifungal activity. The results suggested that the ethoxycarbonyl group at the 2 position and the imine moiety on the seven-membered ring are essential for activity. The most potent of the synthesized analogues (7a, 7b) were further studied by evaluating their cytotoxicity and mode of action (for 7a). The results showed that compounds 7a and 7b were relatively safe for BV2 cells, but compound 7a interfered with Cryptococcus neoformans cell wall integrity by increasing the chitinase activity. Therefore, compound 7a was considered safe as an antifungal agent for animal cells. 相似文献
30.