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41.
Pb(18‐crown‐6)Cl2 and Hg(18‐crown‐6)I2 are obtained as transparent colourless crystals of needle and hexagonal shape, respectively, by isothermal evaporation of their dichloromethane solutions. Pb(18‐crown‐6)Cl2 crystallizes with the trigonal crystal system [ , no. 148, a = b = 1176.3(2), c = 1191.8(3) pm, V = 1428.2(5) 106·pm3, Z = 3] whereas Hg(18‐crown‐6)I2 crystallizes with the orthorhombic crystal system (Pnma, no. 62, a = 1613.9(2) pm, b = 2822.2(5) pm, c = 841.3(1) pm, V = 3832(1)106·pm3, Z = 8). Both compounds are characterized by linear MX2 (HgI2 or PbCl2) molecular units which are encrypted by the crown ether. In both cases, the divalent metal ion resides in the middle of the crown ether resulting in a hexagonal bipyramidal coordination environment for the metal cations. The molecular symmetry comes close to D3d. Hg(18‐crown‐6)I2 and Pb(18‐crown‐6)Cl2 differ in the way the single MX2@18‐crown‐6 units are packed. Whereas the Hg(18‐crown‐6)I2 molecules are arranged in a (distorted) cubic closest packing, the Pb(18‐crown‐6)Cl2 molecules adopt a hexagonal closest packing. 相似文献
42.
André Gustavo de A. Fernandes Pedro Ivo da S. Maia Elizeu J. de Souza Sebastião S. Lemos Alzir A. Batista Ulrich Abram Javier Ellena Eduardo E. Castellano Victor M. Deflon 《Polyhedron》2008
Novel rhenium complexes containing the maltolate (mal) or kojate (koj) anions as chelating ligands have been synthesized: [ReOCl(mal)2] (1), [ReOCl2(mal)(PPh3)] (2), [ReOBr2(mal)(PPh3)] (3), [ReOCl2(koj)(PPh3)] (4) and [ReOBr2(koj)(PPh3)] (5). The products have been characterized by FTIR, 1H, 13C, and 31P NMR spectroscopies and elemental analysis. The crystal and molecular structures of all complexes were determined. Complex 1 crystallizes monoclinic, space group C2/c, Z = 8. It contains two O,O′-bidentate maltolate ligands and one chloro ligand at the (ReO)3+ unit, so that a distorted octahedral geometry is adopted by the six-coordinated rhenium(V) center. The chloro ligand occupies a cis position to the oxo ligand. Complexes 2 and 3 are isostructural and crystallize orthorhombic, space group Pbca and Z = 8. The isostructural complexes 4 and 5 crystallize monoclinic, space group P21/n and Z = 4. In complexes 2–5, the (ReO)3+ unit is coordinated by a monoanionic O,O-bidentate unit of the maltolate (2 and 3) or kojate (4 and 5) ligand, one triphenylphosphine and two halogeno ligands (Cl in 2 and 4; Br in 3 and 5), with the rhenium(V) center in a distorted octahedral environment. The halide ligands are in cis positions to each other. 相似文献
43.
Zhiyu Wang Dr. Xiaoming Wang Zhongwei Chen Dr. Yang Liu Huilin Xie Jie Xue Prof. Lingling Mao Prof. Yanfa Yan Prof. Haipeng Lu 《Angewandte Chemie (International ed. in English)》2023,62(17):e202215206
Introducing chirality into the metal-halide hybrids has enabled many emerging properties including chiroptical activity, spin-dependent transport, and ferroelectricity. However, most of the chiral metal-halide hybrids to date are non-emissive, and the underlying mechanism remains elusive. Here, we show a new strategy to turn on the circularly polarized luminescence (CPL) in chiral metal-halide hybrids. We demonstrate that alloying Sb3+ into chiral indium-chloride hybrids dramatically increases the photoluminescence quantum yield in two new series of chiral indium-antimony chlorides. These materials exhibit strong CPL signals with tunable energy and a high dissymmetry factor up to 1.5×10−2. Mechanistic studies reveal that the emission originates from the self-trapped excitons centered in 5s2 Sb3+. Moreover, near-ultraviolet pumped white light is demonstrated with a polarization up to 6.0 %. Our work demonstrates new strategies towards highly luminescent chiral metal-halide hybrids. 相似文献
44.
Sylvain Sudan Damien W. Chen Cesare Berton Farzaneh Fadaei-Tirani Kay Severin 《Angewandte Chemie (International ed. in English)》2023,62(9):e202218072
A water-soluble coordination cage was obtained by reaction of Pd(NO3)2 with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka=1.8(±0.1)×105 M−1. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br− and I− compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand. 相似文献
45.
Husáková L Cernohorský T Srámková J Hubácková K Dolezalová I 《Analytica chimica acta》2008,614(1):38-45
The mixture of palladium (chloride) with citric acid and lithium is proposed as a new chemical modifier for the elimination of interference occurred during the determination of Tl in aqua regia extracts from rocks, soils and sediments by electrothermal atomic absorption spectrometry using instrumentation with deuterium-lamp background correction (D2-ETAAS). Palladium was preferred to rhodium and platinum as to analyte stabilization, citric acid served as an effective reducing agent facilitating formation of Pd-Tl stable covalent bonds playing an important role in the analyte stabilization. Citric acid in addition helps to remove most of interfering chloride at low temperature. The further addition of Li increased significantly the robustness of chemical modifier against strongly interfering ZnCl2 matrix by binding free chlorine into a more stable LiCl molecule. In the presence of the proposed chemical modifier the temperature for the final step of pyrolysis was adjustable up to 1000 °C, without any noticeable loss of volatile Tl species and the interference of the rest chloride matrix was significantly reduced. The application of the modifier to direct determination of Tl in aqua regia extracts from rocks, soils and sediments has ensured the characteristic mass and LOD value for the original sample 13 pg and 0.043 μg g−1, respectively (10-μL aliquots of sample) and has enabled the use of matrix-free standard solutions for attaining accurate analysis. The accuracy was verified by the analysis of certified reference samples and by the comparison of results with those found by an inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometer (ICP-oa-TOFMS) method. 相似文献
46.
高分子载体催化剂的研究和开发日益受到重视。四氯化锡是一种常用的强Iewis酸,在空气中强烈水解而产生大量盐酸烟雾,保存和使用都不方便,我们曾将四氯化锡与聚苯乙烯交联白球反应制成了一种高分子载体催化剂,对酯化、缩醛、缩酮等有机反应有良好的催化性能,但它在反应中洗脱流失严重,重复使用性能很差,基本上是十种高分子保护型的载体催化剂。为了改善其稳定性,从而提高重复使用性能,我们合成了含有富电子基团的新高分子载体,使四氯化锡与载体中的富电子基团形成较稳定的复合物,使之既保持良好的催 相似文献
47.
通过大角度X射线散射分析,求出了新型无机离子交换剂六偏磷酸锡的径向分布函数,推断其化学结构。应用此结构较好地解释了交换剂的离子交换性质。 相似文献
48.
Pr4S3[Si2O7] and Pr3Cl3[Si2O7]: Derivatives of Praseodymium Disilicate Modified by Soft Foreign Anions For synthesizing both the disilicate derivatives Pr4S3[Si2O7] and Pr3Cl3[Si2O7], Pr, Pr6O11 and SiO2 are brought to reaction with S and PrCl3, respectively, in suitable molar ratios (850 °C, 7 d) in evacuated silica tubes. By using NaCl as a flux, Pr4S3[Si2O7] crystallizes as pale green, transparent single crystals (tetragonal, I41/amd, a = 1201.6(1), c = 1412.0(2) pm, Z = 8) with the appearance of slightly compressed octahedra. On the other hand, Pr3Cl3[Si2O7] emerges as pale green, transparent platelets and crystallizes monoclinically (space group: P21, a = 530.96(6), b = 1200.2(1), c = 783.11(8) pm, β = 109.07(1)°, Z = 2). In both crystal structures ecliptically conformed [Si2O7]6– units of two corner‐linked [SiO4] tetrahedra with Si–O–Si bridging angles of 131° in the sulfide and 148° in the chloride disilicate are present. In Pr4S3[Si2O7] both crystallographically independent Pr3+ cations show coordination numbers of 8 + 1 (5 S2– and 3 + 1 O2–) and 9 (3 S2– and 6 O2–). For Pr1, Pr2 and Pr3 in Pr3Cl3[Si2O7] coordination numbers of 10 (5 Cl– and 5 O2–) and 9 (2 ×; 4 Cl– and 5 O2– or 3 Cl– and 6 O2–, respectively) occur. 相似文献
49.
Pr(BO2)3 and PrCl(BO2)2: Two Praseodymium meta‐Borates in Comparison Single‐crystalline PrCl(BO2)2 can be obtained by the reaction of praseodymium, Pr6O11 and PrCl3 with a small excess of B2O3 in evacuated silica tubes after seven days at 850 °C. If NaCl is additionally used as flux, single crystals of Pr(BO2)3 dominate the main product. Both praseodymium(III) meta‐borates are air and water stable. The crystals of PrCl(BO2)2 emerge as long, thin, pale green needles which tend to severe twinning due to their fibrous habit. The crystal structure (triclinic, P1¯; a = 420.56(4), b = 655.42(7), c = 808.34(8) pm, α = 82.361(8), β = 89.173(9), γ = 71.980(7)°, Z = 2) exhibits zigzag chains {[(B1)ot1/1Oe2/2(B2)Ot1/1Oe2/2]2−} (≡ {[BO2]−}) of corner‐linked [BO3]3− triangles with syndiotactic orientation of the terminal oxygen atoms which are running parallel to the [100] direction. The Pr3+ cations are surrounded by three Cl− and seven O2− anions with the shape of a tetracapped trigonal prism. The green, transparent crystals of Pr(BO2)3 (monoclinic, C2/c; a= 984.98(9), b = 809.57(8), c = 641.02(6) pm, β = 126.783(9)°, Z = 4) appear either lath‐shaped or rather spherical. In the crystal structure the B3+ cations reside both in trigonal planar as well as in tetrahedral coordination of oxygen atoms. Both types of borate polyhedra ([BO3]3− and [BO4]5−) are linked via corners to form chains of the composition {[(B2)‐Ot1/1Oe2/2(B1)Oe4/2(B2)Ot1/1Oe2/2]3−} (≡ {[BO2]−}) which run parallel [101]. The coordination sphere of the Pr3+ cations consists of ten oxide anions which build up a bicapped square antiprism. 相似文献
50.
(NH4)2[Mo6Cl14] · H2O ( 1 ) was prepared from reactions of MoCl2 in ethanol with aqueous NH4Cl solution. It crystallizes in the monoclinic space group I2/a (no. 15), Z = 4 with a = 912.3(1), b = 1491.2(2), c = 1724.8(2) pm, β = 92.25(1)°; R1 = 0.023 (based on F values) and wR2 = 0.059 (based on F2 values), for all measured X‐ray reflections. The structure of the cluster anion can be given as [(Mo6Cl)Cl]2– (i = inner, a = outer ligands). Thermal stability studies show that 1 loses crystal water followed by the loss of NH4Cl above 350 °C to yield MoCl2. The water‐free compound (NH4)2[Mo6Cl14] ( 2 ) was synthesized by solid state reaction of MoCl2 and NH4Cl in a sealed quartz ampoule at 270 °C. No single‐crystals could be obtained. Decompositions of 1 and 2 under nitrogen and argon exhibited the loss of NH4Cl at about 350 °C. Decomposition under NH3 resulted in the formation of MoN and Mo2N at 540 °C and 720 °C, respectively. 相似文献