共查询到20条相似文献,搜索用时 15 毫秒
1.
Na R Jing C Xu Q Jiang H Wu X Shi J Zhong J Wang M Benitez D Tkatchouk E Goddard WA Guo H Kwon O 《Journal of the American Chemical Society》2011,133(34):13337-13348
In this paper we describe the phosphine-catalyzed [3 + 2], [3 + 3], [4 + 3], and [3 + 2 + 3] annulations of azomethine imines and allenoates. These processes mark the first use of azomethine imines in nucleophilic phosphine catalysis, producing dinitrogen-fused heterocycles, including tetrahydropyrazolo-pyrazolones, -pyridazinones, -diazepinones, and -diazocinones. Counting the two different reaction modes in the [3 + 3] cyclizations, there are five distinct reaction pathways-the choice of which depends on the structure and chemical properties of the allenoate. All reactions are operationally simple and proceed smoothly under mild reaction conditions, affording a broad range of 1,2-dinitrogen-containing heterocycles in moderate to excellent yields. A zwitterionic intermediate formed from a phosphine and two molecules of ethyl 2,3-butadienoate acted as a 1,5-dipole in the annulations of azomethine imines, leading to the [3 + 2 + 3] tetrahydropyrazolo-diazocinone products. The incorporation of two molecules of an allenoate into an eight-membered-ring product represents a new application of this versatile class of molecules in nucleophilic phosphine catalysis. The salient features of this protocol--the facile access to a diverse range of nitrogen-containing heterocycles and the simple preparation of azomethine imine substrates--suggest that it might find extensive applications in heterocycle synthesis. 相似文献
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Habibul Arfin Jagjit Kaur Tariq Sheikh Assist. Prof. Sudip Chakraborty Assoc. Prof. Angshuman Nag 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11403-11407
Bi3+ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi3+ and lanthanide ions. Codoping of Bi3+ and Ln3+ (Ln=Er and Yb) in Cs2AgInCl6 double perovskite is presented. Bi3+-Er3+ codoped Cs2AgInCl6 shows Er3+ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi3+ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi3+-Er3+ codoped Cs2AgInCl6 shows ca. 45 times higher emission intensity compared to the Er3+ doped Cs2AgInCl6. Similar results are also observed in Bi3+-Yb3+ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes. 相似文献
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Wang X Liu L Nie Q Xu T Shen X Dai S Zhang X 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(3-4):1025-1029
Up-conversion luminescence characteristics under 975 nm excitation have been investigated with Tb3+/Tm3+/Yb3+ triply doped tellurite glasses. Here, green (547 nm: (5)D(4)-->(7)F(4)) and red (660 nm: (5)D(4)-->(7)F(2)) up-conversion (UC) luminescence originating from Tb3+ is observed strongly, because of the quadratic dependences of emission intensities on the excitation power. Especially, the UC luminescence was intensified violently with the energy transfer from the Tm3+ ions involves in the Tb3+ excitation. To the Tb3+/Tm3+/Yb3+ triply doped glass system, a novel up-conversion mechanism is proposed as follows: the energy of (3)G(4) level (Tm3+) was transferred to (5)D(4) (Tb(3+)) and the 477-nm UC luminescence of Tm3+ was nearly quenched. 相似文献
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F. Hagelberg 《International journal of quantum chemistry》2001,85(2):72-84
The origin of the pseudoprecession phenomenon is investigated through a computational study of the time evolution of H3+ and Li3+ by electron nuclear dynamics theory. In particular, the pseudorotation of both molecules is shown to induce a spatial rotation, which in turn leads to Coriolis coupling of the two orthogonal nuclear shape deformation modes. This effect is rooted in an anisotropy of the molecular ground state potential energy surface that is caused by the interaction between the D3h ground state and a twofold degenerate first excited state. Computations are performed for a variety of vibrational energies. In addition, the impact of the anharmonicity of the ground state potential surface on the shape deformation modes and the coupling between them is discussed. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
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Speghini A Francini R Martinez A Tavernese M Bettinell M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(10):2001-2008
The absorption and emission spectroscopies of Er3+ doped and Er3+/Yb3+ codoped Ca(PO3)2, Sr(PO3)2 and Ba(PO3)2 glasses have been studied. From the Judd-Ofelt intensity parameters, the spontaneous emission probabilities of some relevant transitions and the radiative lifetimes of several excited states of Er3+ have been calculated. The decay curves of the Er3+ emission at 1.5 microm have been measured at different temperatures. The data have been fitted using a stretched exponential function and the obtained experimental lifetimes have been compared with the calculated radiative lifetimes. The difference between the experimental and calculated lifetimes is attributed to the presence of traces of OH groups in the host glasses. The absolute OH content in some glasses has been determined from the infrared spectra. The emission spectra at 1.5 microm of the Er3+ ion in the codoped glasses have been measured at different temperatures. The integrated emission intensities decrease significantly on passing from room temperature to 13 K, suggesting a temperature dependence of the rate of the energy transfer process between Yb3+ and Er3+. 相似文献
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Intensity parameters of Sm3+ in borate glasses were obtained by fitting the oscillator strengths to the Judd-Ofelt formula and a study of energy transfer from gadolinium to samarium was performed. An increase of samarium fluorescence originating from the level was observed in the presence of gadolinium, in the concentration range of 0.1–3 wt% samarium with gadolinium constant at 3 wt%. The intensity of samarium fluorescence on excitation at 273 nm increased by one order of magnitude in the presence of gadolinium. From the excitation spectrum of the double-doped glasses (Gd + Sm), it was deduced that energy absorbed by gadolinium is transferred from gadolinium levels to the and samarium levels.The mechanism of this energy transfer was obtained by plotting the energy transfer probabilities as a function of samarium concentration. A linear dependence of (η intensity of gadolinium in the presence of samarium) versus square of concentration of Sm + Gd is obtained. From this it is concluded that the transfer is of electric-multipolar type, mainly dipole-dipole. A small increase (about 10%) of fluorescence of samarium in the presence of gadolinium excited at levels where no energy transfer can take place is attributed to the fact that the quenching of samarium occurring by the cross relaxation is suppressed by the presence of gadolinium as seen from concentration dependence of samarium doped glasses compared to double-doped glasses. 相似文献
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The structural and optical properties of the Er3+-Tm3+-Yb3+codoped CaMoO4 phosphors prepared by chemical route have been explored. The crystalline structures of the prepared phosphors have been investigated with the help of X-ray diffraction analysis. The presence of different vibrational modes and absorption bands arising due to the transitions from the ground state to different excited states of rare earth ions have been identified using the Raman and UV-VIS-NIR absorption spectra of the developed phosphor, respectively. The concentration quenching effect on the luminescence property of the prepared materials has been explained in detail. The upconversion luminescence property of the Er3+-Tm3+-Yb3+codoped CaMoO4 phosphor annealed at different temperatures under 980 nm and 808 nm excitations have been reported. The energy transfer Er3+ → Tm3+, Yb3+ → Er3+ and Tm3+ has been found to be responsible for efficient UC emission. The dipole-dipole interaction is observed to be responsible for the concentration quenching of the luminescence intensity. The effect of annealing temperature on the upconversion luminescence property has been explained in detail. The results suggest that the developed tri-doped phosphor may be suitable in making the efficient NIR to visible upconverter and lighting based optical devices. 相似文献
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Kumar K Rai SB Rai A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,71(2):508-512
Energy transfer excited upconversion emission in Nd3+/Pr3+-codped tellurite glass have been studied on pumping with 800 nm wavelength. The upconversion emission bands from Pr3+ ion are observed at the 488, 524, 546, 612, 647, 672, 708 and 723 nm due to the (3P0 + 3P1)-->3H4, 3P1-->3H5, 3P0-->3H5, 3P0-->3H6, 3P0-->3F2, 3P1-->3F3, 3P0-->3F3 and 3P0-->3F4 transitions, respectively. The addition of ytterbium ions (Yb3+) on the upconversion emission intensity is also studied and result shows an eight times enhancement in the upconversion intensity at 488 nm from Pr3+ ions. The pump power and concentration dependence studies are also made. It is found that Yb3+ ions transfer its excitation energy to Nd3+ from which it goes to Pr3+. No direct transfer to Pr3+ is seen. This is verified by codoping Nd3+ and Pr3+ into the host. 相似文献
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Quantum yields of Ce3+ in borax glasses were obtained by the comparative method and by lifetime measurements. Energy transfer from Ce3+ to Tb3+ was detected in borax glasses from the excitation spectrum. The transfer probabilities were calculated from the increase in the Tb3+ fluorescence in the presence of Ce3+ and the decrease of the Ce3+ fluorescence in the presence of Tb3+. A linear dependence of the transfer probabilities was found with the squared sum of the concentrations of the donor and acceptor ions. This is consistent with dipolar mechanism and interactions of one Ce3+ donor with two Tb3+ acceptors, in view of the Fong-Diestler theory. 相似文献
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By using a hydrothermal method, a series of Eu3+ concentration dependent GdF3 nanocrystals have been synthesized. The crystalline structures of samples are characterized by XRD patterns, the morphology and size of the samples are illustrated by FE-SEM images, and the optical properties of the samples are presented by PL excitation and emission spectra. The energy transfer from host Gd3+ to Eu3+ is observed in the Eu3+ doped GdF3 nanocrystals. The optical properties of Eu3+ and the energy transfer efficiency from host Gd3+ to Eu3+ are discussed on the basis of the Eu3+ concentration dependent integrated PL excitation and emission spectra of Gd3+ and Eu3+. The discussion on optical properties of Eu3+ and the energy transfer from Gd3+ to Eu3+ is meaningful to design and synthesize Gd3+ based compounds. 相似文献
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Ce3+、Tb3+离子及Ce3+-Tb3+离子对在Sr4Si3O8Cl4基质中发光的研究 总被引:4,自引:1,他引:3
研究了Ce3+、Tb3+、离子及Ce3+-Tb3+离子对在Sr4Si3O8Cl4基质中的发射光谱和激发光谱。初步讨论了Ce3+、Tb3+离子之间发光敏化的机理。 相似文献
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首先用水热法合成了NaNbO3样品,然后用固相法分别合成了NaNbO3,NaNbO3:Er3+,NaNbO3:Sm3+样品,X射线衍射结果表明所制备的粉体NaNbO3(水热法200℃和固相法900℃退火),NaNbO3:Er3+(900℃退火),NaNbO3:Sm3+(900℃退火)为立方相结构,在退火温度800,950和1000℃时是正交晶系,长方体结构.该粉末在980 nm LD激发下,分别发射出中心波长约为526 nm绿色,547nm绿色和662 nm红色(掺Er3+)、526 nm绿色,550 nm绿色和660 nm红色(掺Sm3+)的上转换荧光.探讨了Er3+,Sm3+的上转换发光机制.研究了晶体的对称性和退火温度对NaNbO3:Er3+样品上转换发光强度的影响,结果表明,随着晶体的对称性降低和退火温度的提高,NaNbO3:Er3+样品的上转换发光强度增强. 相似文献
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采用水热法制备了Er3 离子浓度为3%,yb3 离子浓度分别为10%,20%的GdF3:Er3 ,Yb3 .XRD结果表明:合成的样品均为正交结构的GdF3,Cd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品的晶粒尺寸分别为28和26 nm.研究了980 nm红外光激发的上转换发射光谱.结果表明:红光和绿光发射分别来自于Er3 离子的2H11/2,4S3/2→4I15/2和4F9/2→4I15/2跃迁.样品的绿光发射强度较红光发射强.但绿光和红光发射的相对强度比例与Yb3 离子浓度有关.对Gd0.87Yb0.10Er0.03F3和Gd0.77Yb0.20Er0.03F3样品中可能的上转换发光机制进行了讨论. 相似文献
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Doped ceria electrolytes of Ce1-aGda-ySmyO2–0.5a, wherein a=0.15 or 0.2, and 0ya, were prepared with the citrate method, and characterized by inductively coupled plasma–atomic emission spectrometry, energy dispersive spectrometry, scanning electron microscopy, powder X-ray diffraction, and AC impedance spectroscopy. The effect of composition on the structure and conductivity was studied. All the samples were fluorite-type ceria-based solid solutions. For the singly doped samples, the optimal composition was Ce0.85Gd0.15O1.925 for Gd3+-doped ceria (CGO), which showed higher ionic conductivity than the best Sm3+-doped ceria (CSO) at 773–973 K. For the co-doped samples, the ionic conductivities were higher than those of the singly doped ones in the temperature range 673–973 K when a=0.15, but only better in 673–773 K when a=0.2. For the samples of Ce0.85Gd0.15-ySmyO1.925, wherein 0.05y0.1, much higher ionic conductivity was observed than those of the singly doped ceria at 773K~973 K. Therefore, these co-doped samples would be better than CGO and CSO to be the electrolytes of intermediate-temperature solid oxide fuel cells. 相似文献
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LI Ming GAO Shu-Lin ZHANG Xiang-Fei XU Ju-Li YU Shi-Wen YAO Li-Feng YIN Li-Qin XIE Xiao-Guang 《结构化学》2008,27(1)
The title reaction proceeds via a one- and two-step mechanism along the 3A" and 3A' surfaces, respectively. The 3A' excited state surface has a lower barrier than the 3A" ground state surface (11.6 and 16.0 kcal/mol, respectively). We suggest that, at low energies, the reaction proceeds along the A' surface and then makes an intersystem crossing to the A" surface and yields the ground state product VO (3∑), which may explain the small VO cross-section at low energies observed in the experiment 相似文献
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