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111.
Hibbs DE Austin-Woods CJ Platts JA Overgaard J Turner P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1075-1084
The experimental electron density distribution in taurine, 2-aminoethane sulfonic acid, 1, has been determined from high-resolution X-ray diffraction data collected at a temperature of 100 K. Taurine crystallizes as a zwitterion in the monoclinic space group P2(1)/c. Topological analysis of the experimental electron density and a comparison with high-level theoretical gas-phase calculations show that the crystal environment has a significant influence on the electronic configuration of the sulfonate moiety in 1, which in the crystal is more delocalized than in the gas phase. This crystal effect is mainly due to hydrogen bonding. 相似文献
112.
Amphiphilic polypyridyl mthenium(Ⅱ) complex cis-di(isothiocyanato)(4,4'-di-tert-butyl-2,2'-bipyridyl)(4,4'- dicarboxy-2,2'-bipyridyl)ruthenium(Ⅱ)(K005) has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer (MLCT) bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru(dcbpy)2(NCS)2, known as the N3 dye, and the amphiphilic ruthenium(Ⅱ) dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode (SCE) with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte. 相似文献
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The absorption spectra and emission spectral band shapes of several polypyridine-ligand (PP) bridged bis-ruthenium(II) complexes imply that the Ru(II)/Ru(III) electronic coupling is weak in their lowest energy metal to ligand charge transfer (MLCT) excited states. Many of these PP-bridging ligands contain pyrazine moieties and the weak electronic coupling of the excited states contrasts to the strong electronic coupling inferred for the correlated mixed-valence ground states. Although the bimetallic complexes emit at significantly lower energy than their monometallic analogs, the vibronic contributions to their 77 K emission spectra are much stronger than expected based on comparison to the monometallic analogs (around twofold in some complexes) and this feature is characteristic of bimetallic complexes in which the mixed-valence excited states are electronically localized. The weaker excited state than ground state donor/acceptor electronic coupling in this class of complexes is attributed to PP-mediated super-exchange coupling in which the mediating orbital of the bridging ligand (PP-LUMO) is partly occupied in the MLCT excited states, but is unoccupied in the ground states; therefore, the vertical Ru(III)-PP− (MLCT) energy is larger and the mixing coefficient smaller in these excited states than is found for Ru(II)-PP in the corresponding ground states. 相似文献
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天线若丹明染料分子内能量与电荷传递的研究 总被引:2,自引:0,他引:2
染料三重态在染料激光的应用中起着重要作用,尤其是三重态一Z重态(T-T)吸收常常会造成谐振腔损耗*.为了减少由基态吸收而造成的话振腔损耗,带有紫外吸收天线分子的三发色团染料已在研究问,2,5·二苯基螨喳(PP0)在紫外区(如308删)有很强的吸收,PPO-rhod.系列染料(见图1)在紫外区的吸收就很强,由PPO到若丹明母体的单线态一单线态(S功能量传递使这类三发色团染料具有较大的荧光量子效率,较小的基态重复吸收耗能卜,司.然而,在610N640nm区域中这些天线若丹明染料的激光输出效率远远小于若丹明Rh630*,其原因正是… 相似文献
116.
Robert S. Pomeroy Jeffrey D. Kolczynski Jonathan V. Sweedler M. Bonner Denton 《Mikrochimica acta》1989,99(3-6):347-353
A unique simultaneous emission spectrograph is utilized to perform qualitative and quantitative analysis on trace quantities of solid particulates. The atomic emission spectroscopic system consists of a direct current plasma source and an echelle spectrograph with a charge injection device detector, enabling the system to simultaneously measure the wavelength range from 220 nm to 520 nm with 0.02 nm resolution at 300 nm. Monitoring all wavelengths simultaneously allows the qualitative and quantitative determination of most major and minor constituent in a trace quantity of sample with little prior knowledge about the sample. The ability to perform qualitative and quantitative analysis on particulates is demonstrated by evaluating NBS certified coal fly ash, as well as a sample taken from the respirator air filter at an acute care unit in a hospital.Presented in part at the 1989 European Winter Conference on Plasma Spectrochemistry, Reutte, Austria 相似文献
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The photophysical processes of 4-formacyl-triphenylamine (FTA) and 4,4'-bisformacyl-triphenyl-amine (BTA) have been studied. The fluorescences of FTA and BTA with donor (triamine) and acceptor (formacyl) moieties show the twisted intramolecular charge transfer (TICT) emission in polar solvents and photoinduced charge transfer (ICT) emission in nonpolar solvents. These could be supported by the solvent effect, temperature effect and the quenching process by strong electron-deficient compounds. 相似文献