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1.
Mn4+ doped and Dy3+, Tm3+ co-doped MgAl2Si2O8-based phosphors were prepared by conventional solid state reaction at 1,300 °C. They were characterized by thermogravimetry, differential thermal analysis, X-ray powder diffraction, photoluminescence, and scanning electron microscopy. The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 600–715 nm and had a different maximum intensity when activated by UV illumination, was discussed. Such a red emission can be attributed to the 2E → 4A2 transitions of Mn4+.  相似文献   

2.
Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages, θS, of a few hundredths of a monolayer (ML), and is most pronounced for 0.1–0.3 ML where the decay rate is increased by a factor of around 30. For θS close to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lower θS is attributed to the formation and diffusion across terraces of Au−S complexes, particularly AuS2 and Au4S4, with some lesser contribution from Au3S4. This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers.  相似文献   

3.
The Zintl anion (Ge2As2)2− represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh3)AuMe] into the 1,2-diaminoethane (en) solution of (Ge2As2)2−, the heterometallic cluster anion [Au6(Ge3As)(Ge2As2)3]3− is obtained as its salt [K(crypt-222)]3[Au6(Ge3As)(Ge2As2)3]⋅en⋅2 tol ( 1 ). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non-bonding) octahedron of six Au atoms that is face-capped by four (GexAs4−x)x (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge3As)3− unit besides three (Ge2As2)2− units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au6(Ge3As)(Ge2As2)3]3−. Reactions of the heavier homologues (Tt2Pn2)2− (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1 , but dimers of ternary nine-vertex clusters, {[AuTt5Pn3]2}4− (in 2 – 4 ; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo-tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge2As2)2−, according to the DFT calculations.  相似文献   

4.
The mechanism of the catalytic hydrolysis of BH4 on Au(111) as studied by DFT is reported. The results are compared to the analogous process on Ag(111) that was recently reported. It is found that the borohydride species are adsorbed stronger on the Au0-NP surface than on the Ag0-NP surface. The electron affinity of the Au is larger than that of Ag. The results indicate that only two steps of hydrolysis are happening on the Au(111) surface and the reaction mechanism differs significantly from that on the Ag(111) surface. These remarkable results were experimentally verified. Upon hydrolysis, only three hydrogens of BH4 are transferred to the Au surface, not all four, and H2 generation is enhanced in the presence of surface H atoms. Thus, it is proposed that the BH4 hydrolysis and reduction mechanisms catalyzed by M0-NPs depend considerably on the nature of the metal.  相似文献   

5.
Photoelectron spectra of (CO2)nH2O? (2≤n≤8) and (CO2)n(H2O) 2 ? (1≤n≤2) were measured at the photon energy of 3.49 eV. The spectra show unresolved broad features, which are approximated by Gaussians. The vertical detachment energies (VDEs) were determined as a function of the cluster size. For (CO2)nH2O?, the VDE-n plots exhibit a sharp discontinuity between n=3 and 4; the VDE value is ≈3.5 eV at n=3, while it drops down abruptly to 2.59 eV at n=4. This discontinuity in VDE is ascribed to "core switching" at n=4; a C2O 4 ? dimer anion forms the core of (CO2)nH2O? for n≤3, while a monomer CO 2 ? is the core for n≥4. The (CO2)2(H2O) 2 ? ion has a VDE of 2.33 eV, indicating the presence of a CO 2 ? monomer core in the binary clusters containing two H2O molecules.  相似文献   

6.
采用从头计算HF,MP2方法和密度泛函理论,对Au(II)系列化合物[Au(CH2)2PH2]2X2(X=F,Cl,Br,I)的几何结构、电子结构和振动频率进行了研究.研究表明Au的5d和6s电子参与Au—Au以及Au—X之间的成键.Au—Au,Au—X键强烈的电子相关作用使HF方法不适于该体系的研究,BP86和B3LYP两种泛函给出较大的Au—Au和Au—X键长,而MP2方法和局域的密度泛函方法则给出了合理的结构参数.局域密度泛函方法计算得到的Au—Au键和Au—X键振动频率也与实验数据符合较好.还运用含时密度泛函理论计算了[Au(CH2)2PH2]2X2的电子激发能,对分子在紫外-可见光谱范围内的电子跃迁进行了分析,考察了卤素配体对激发能的影响,并结合分子轨道能级的变化对此给予了解释.  相似文献   

7.
The N-heterocyclic carbene (NHC) precursor, 1-(2-aminoethyl)-3-methylimidazolium nitrate, [NH(2)(CH(2))(2)imMe)]NO(3) ([3][NO(3)]) reacted with Ag(2)CO(3) in dimethyl sulfoxide readily yielding a Ag(I)-(NHC-NH(2)) complex presenting limited stability in solution. The in situ carbene transfer reaction of the latter with [Au(tht)Cl] afforded the first example of a dinuclear gold(I) complex [Au(2)(NH(2)(CH(2))(2)imMe)(2)][NO(3)](2) ([5][NO(3)](2)) bearing a primary amino-functionalized NHC ligand. The complex has been characterized by NMR, mass spectrometry, X-ray crystallography and cyclic voltammetry; the electrochemical behaviour and photophysical properties of [5][NO(3)](2) have been also investigated and the experimental data have been compared with density functional theory (DFT) and Time Dependent (TDDFT) calculations. Single-crystal structural studies showed that the Au(I)-carbene compound contains dinuclear (AuL)(2) cations in which pairs of gold(I) centres are linked by a pair of bridging ligands, with a Au···Au aurophilic contact of 3.2332(17) ? that is maintained in solution as documented by the DFT calculations. Complex [5][NO(3)](2) is photoluminescent in solution at room temperature and the high energy emission peak at 410 nm is remarkably shifted with respect to the absorption band centered at 260 nm.  相似文献   

8.
Excitation functions for the production of198mAu,198Au,198(m+g)Au, by (, 2pn) reactions on gold and isomeric ratios for198Au were determined experimentally. The method of activation of metallic foils was employed. The irradiations were performed in the isochronous cyclotron at Karlsruhe (Germany) with -particles at 90 MeV. Gamma-spectrometry by means of an intrinsic Ge detector was used to determine the nuclides produced. In addition, a comparison between the cross sections obtained and a calculation using the hybrid model of pre-equilibrium reactions, in combination with the statistical model development by ERNST is presented.  相似文献   

9.
Intramolecular π-aromatization is a trait of many organic compounds that enhances the stability of their structures and polarizes related C−C π bonds. In contrast, rare study is focused on this phenomenon in metal clusters. Many existing homometallic clusters exhibit aromaticity, often characterized by nonpolar metal-metal bonds and a high degree of symmetry. However, synthesizing low-symmetric homometallic clusters with high-polar metal-metal bonds is challenging due to their limited thermodynamic stability. Herein, we report a facile strategy for the synthesis of [Au(μ2-ER2)]3−AuPMe3 (E=Ge, Sn; R2=1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl) clusters and reveal a novel stabilization mode, intramolecular σ-aromatization. Our electronic structure analyses show that these low-symmetric clusters possess a ten-electron σ-aromatic system, which is achieved via intramolecular σ-aromatization. Moreover, the strength of σ-aromaticity gives rise to a polarity-tunable exo-Au−Au bond.  相似文献   

10.
Reactions of gold anions and cations generated by laser desorption/ionization were studied in the FTICR spectrometer. Au associated with C6F6 to give the novel Au(C6F6) complex, whose binding energy was estimated to be 24 ± 4 kcal mol−1 from analysis of the radiative association (RA) kinetics. Au+ associated with C6F5H to give Au+(C6F5H), with binding energy estimated to be 31 kcal mol−1. Au+ reacted with C6H6 to form the well known Au+(C6H6) and Au+(C6H6)2 complexes. The observation of rapid charge transfer from Au+(C6H6) to C6H6 was interpreted as showing that benzene binds more strongly to neutral Au than to Au+. The neutral Au–C6H6 bond is accordingly concluded to be stronger than about 70 kcal mol−1.  相似文献   

11.
Two supramolecular complexes, {{Ni(H2O)(phen)2[Au(CN)2]}[Au(CN)2]?·?1.5H2O} n (1) (phen?=?1,10-phenanthroline) and [H2teta][Au2(CN)4]?·?2H2O (2) (teta?=?5,7,7,12,14,14-hexamethyl-1,4,8,11-tetra-azacyocloteradeca-4,11-diene) have been synthesized and structurally characterized. Complex 1 was a one-dimensional infinite chain constructed by [Au(CN)2]? building blocks. In complex 2, there are one cation, one anion, and two water molecules in the asymmetric unit. The two complexes are interconnected through a combination of aurophilic attractions and hydrogen bonds and formed into 3D supramolecular structures. The aqueous solutions of 1 and 2 display interesting luminescence at room temperature.  相似文献   

12.
Kita  Ewa 《Transition Metal Chemistry》2001,26(4-5):551-556
Two [Cr(C2O4)2(AB)]2– type complexes, obtained from the reaction of cis-[Cr(C2O4)2(H2O)2] with the AB ligand, [AB = picolinic (pyac) or 2-pyridine-ethanoic acid (pyeac) anions], were converted into [Cr(C2O4)(pyac)(H2O)2]0 and [Cr(C2O4)(pyeac)(H2O)2]0 compounds, respectively via FeIII-induced substitution of the oxalato ligand. The aquation products were separated chromatographically and their spectral characteristics and acid dissociation constants determined. The kinetics of the oxalato ligand substitution were studied with a 10–40 fold excess of FeIII over [CrIII] at [H+] = 0.2 M and at constant ionic strength 1.0 M (Na+, H+, Fe3+, ClO 4). The reaction rate law is of the form: r = k obs[CrIII], where k obs = kQ[FeIII]/(1 + Q[FeIII]). The first-order rate constants (k), preequilibria quotients (Q) and activation parameters derived from the k values have been determined. The reaction mechanism is discussed in terms of a Lewis acid catalyzed (induced) ligand substitution.  相似文献   

13.
The reaction of hexachlorophosphazene, P3N3Cl6, with SO3 and the gold halides AuCl3 and AuBr3, respectively, leads to the new cyclic anionic tetramer, [S4N2O10]2−, which is coordinated to Au3+ in the dimeric complexes [Au2X2(S4N2O10)2] (X=Cl, Br). The [S4N2O10]2− anion can be seen as the condensation product of two sulfate anions, [SO4]2−, and two amidosulfate anions, [NH2SO3].  相似文献   

14.
Quasi-one-dimensional (1D) solid solutions Ti1 ? x Fe x (OCH2CH2O)2 ? x/2 (0 < x ≤ 0.1) with the structure of anatase were prepared by heating the glycolate Ti1 ? x Fe x (OCH2CH2O)2 ? x/2 in an atmosphere of air at a temperature of >450°C. The conditions of formation and the properties of the new glycolate Ti3Fe2(OCH2CH2O)9 were described. It was found that the synthesized Ti1 ? x Fe x O2 ? 2x/2 solid solutions exhibit photocatalytic activity in the reaction of hydroquinone oxidation in an aqueous solution on irradiation with UV light. A correlation between the rate of oxidation of hydroquinone and the concentration of iron in the catalyst was established. A procedure for the preparation of titanium dioxide with the structure of anatase doped with iron and carbon (Ti1 ? x Fe x O(2 ? x/2) ? yCy) and also composites on its basis, which contain an excess amount of carbon, was proposed.  相似文献   

15.
The picolyl-substituted NHC complex [Au(im(CH(2)py)(2))(2)]PF(6) (1) reacts with two equivalents of copper(I) halides, affording compounds [Au(im(CH(2)py)(2))(2)(CuX)(2)]PF(6) (X = Cl, 2; Br, 3; I, 4). Each complex contains a nearly linearly coordinated [Au(NHC)(2)](+) center where the two picolyl groups on each im(CH(2)py)(2) ligand chelate a single copper atom. The Cu(I) center resides in a distorted tetrahedral environment and is coordinated to two pyridyl groups, a halide ion, and a gold metalloligand. The Au(I)-Cu(I) separations measure 2.7030(5), 2.6688(9), and 2.6786(10) ? for 2-4, respectively. Additionally, each Cu(I) center is further coordinated by a semibridging NHC ligand with short Cu-C separations of ~2.3 ?. In solution, these complexes dissociate the Cu(I) ion. In the solid state, 2-4 are photoluminescent with respective emission maxima of 512, 502, and 507 nm. The reaction of [Au(im(CH(2)py)(2))(2)]PF(6) with four equivalents of CuBr afforded the coordination polymer {[AuCu(2)Br(2)(im(CH(2)py)(2))(2)]Br·3CH(3)CN}(n) (5). This polymeric complex contains [Au(NHC)(2)](+) units interconnected by Cu(2)Br(2) dimers. In 5, the Au-Cu separations are long at 4.23 and 4.79 ?, while the Cu-Cu distance is considerably shorter at 2.9248(14) ?. In the solid state, 5 is photoluminescent with a broad band appearing at 533 nm.  相似文献   

16.
We have implemented a model of I 2 ? (CO2) n (2 ≤n ≤ 17) clusters and present an analysis of the minimum energy structures obtained from a quenching procedure. A discussion of the importance of various potential contributions to the energetics of the clusters is also presented. Given the current state of understanding of structural control of caging and the time scales of recombination and evaporation, this model has important implications for understanding the picosecond dynamics observed by the Lineberger group and for rigorous studies of evaporation rates.  相似文献   

17.
A new ternary cluster anion [Au(η~2-Sn_2Sb_2)_2]~(3-) was synthesized and identified. The electronic structure of [Au(η~2-Sn_2Sb_2)_2]~(3-) was analyzed by means of DFT calculations. The electronic energy and energy gap indicate that [Au(η~2-Sn_2Sb_2)_2]~(3-) features coplanar faces AuSn_2 in which gold is directly coordinated by four tin atoms. Molecule orbital composition analysis indicates that d-orbital in Au atom contributes to bonding. Charge decomposition analysis(CDA) shows that electron donation and back donation are the key factors forming planar conformation of Au atom in [Au(η~2-Sn_2Sb_2)_2]~(3-). Meanwhile, the calculated Mayer bond order indicates relatively weaker interactions between Au and coordinated tetrahedral [Sn_2Sb_2]~(2-).  相似文献   

18.

Two anionic complexes of Au(III) with the bioligand biuret, cis-[Au(Biu)X2]? (BiuH2=biuret, X=Cl, Br), have been synthesized and characterized. The molecular structure of cis-[Au(Biu)Br2]PPh4 has been determined by X-ray diffraction analysis. The complex anion has square-planar geometry with one deprotonated biuret dianion coordinated bidentately to the metal center via the terminal amino nitrogen atoms and two bromide ions in cis positions. There are no significant intermolecular Au-Au interactions in the solid state. Ab initio calculations of the geometric structure at different computational levels for biuret and both anionic complexes as well an IR study of the structures obtained are performed.  相似文献   

19.
合成了2个蒽基配合物[Au(anbdtim)2]PF6 (1)和[Au(anbdtim)2][Au(CN)2] (2),其中anbdtim=2-蒽基-4,5-双(2,5-二甲基(3-噻吩基))-1-甲基咪唑。它们含有不同的抗衡阴离子,1中的为PF6-2中的为[Au(CN)2]-。这导致2个配合物在溶液和固态中都表现出显著不同的荧光。在CH2Cl2溶液中,配合物12的荧光发射波长分别为465和445 nm。在固态,12的荧光发射波长分别为 450和 478 nm。有趣的是,配合物 2对苯分子很敏感,它在苯中的荧光发射波长为 475 nm(量子产率 Φ=66.5%),在 CH2Cl2中为448 nm(Φ=22.9%)。此外,我们利用配合物2的苯溶液蒸发制备了蓝绿色发光固体2-benzene。当交替地除去和再次加入苯,固体 2-benzene的荧光发射在蓝绿色(491 nm)和钢蓝色(460 nm)之间可逆地转换。在实验结果的基础上,我们讨论了抗衡阴离子和苯分子对12的发光行为的影响。  相似文献   

20.
合成了2个蒽基配合物[Au (anbdtim)2]PF6(1)和[Au (anbdtim)2][Au (CN)2](2),其中anbdtim=2-蒽基-4,5-双(2,5-二甲基(3-噻吩基))-1-甲基咪唑。它们含有不同的抗衡阴离子,1中的为PF6-,2中的为[Au (CN)2]-。这导致2个配合物在溶液和固态中都表现出显著不同的荧光。在CH2Cl2溶液中,配合物12的荧光发射波长分别为465和445 nm。在固态,12的荧光发射波长分别为450和478 nm。有趣的是,配合物2对苯分子很敏感,它在苯中的荧光发射波长为475 nm (量子产率Φ=66.5%),在CH2Cl2中为448 nm (Φ=22.9%)。此外,我们利用配合物2的苯溶液蒸发制备了蓝绿色发光固体2-benzene。当交替地除去和再次加入苯,固体2-benzene的荧光发射在蓝绿色(491 nm)和钢蓝色(460 nm)之间可逆地转换。在实验结果的基础上,我们讨论了抗衡阴离子和苯分子对12的发光行为的影响。  相似文献   

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