全文获取类型
收费全文 | 6264篇 |
免费 | 1010篇 |
国内免费 | 985篇 |
专业分类
化学 | 4707篇 |
晶体学 | 112篇 |
力学 | 65篇 |
综合类 | 66篇 |
数学 | 715篇 |
物理学 | 607篇 |
无线电 | 1987篇 |
出版年
2024年 | 16篇 |
2023年 | 101篇 |
2022年 | 178篇 |
2021年 | 260篇 |
2020年 | 331篇 |
2019年 | 277篇 |
2018年 | 206篇 |
2017年 | 275篇 |
2016年 | 346篇 |
2015年 | 349篇 |
2014年 | 510篇 |
2013年 | 569篇 |
2012年 | 499篇 |
2011年 | 440篇 |
2010年 | 344篇 |
2009年 | 386篇 |
2008年 | 400篇 |
2007年 | 394篇 |
2006年 | 360篇 |
2005年 | 320篇 |
2004年 | 270篇 |
2003年 | 256篇 |
2002年 | 226篇 |
2001年 | 150篇 |
2000年 | 119篇 |
1999年 | 82篇 |
1998年 | 74篇 |
1997年 | 90篇 |
1996年 | 66篇 |
1995年 | 66篇 |
1994年 | 58篇 |
1993年 | 36篇 |
1992年 | 49篇 |
1991年 | 38篇 |
1990年 | 28篇 |
1989年 | 27篇 |
1988年 | 14篇 |
1987年 | 14篇 |
1986年 | 9篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有8259条查询结果,搜索用时 10 毫秒
41.
本文概述了配位聚合载体化催化剂的ESR研究进展,介绍了载体研究、活性中心研究及计算机模拟技术研究方面的发展概况. 相似文献
42.
D. N. Dybtsev M. P. Yutkin E. V. Peresypkina A. V. Virovets Y. Hasegawa H. Nishihara V. P. Fedin 《Russian Chemical Bulletin》2007,56(9):1782-1786
The reaction of Co(NO3)2·6H2O with 1,3,5-benzenetricarboxylic acid (H3btc, trimesic acid) in DMF at 100 °C afforded the coordination polymer [Co3(dmf)6(btc)(Hbtc)(H2btc)]··9H2O (1) (dmf is N,N′-dimethylformamide, DMF). According to the X-ray diffraction study, the metal-organic coordination polymer is composed of
planar honeycomb (6,3) networks, in which the organic benzenetricarboxylate anions and the inorganic Co2+ cations play a role of three-connected nodes. Disordered water molecules are intercalated between the layers. A study of
the magnetic properties showed the presence of a weak antiferromagnetic coupling between the Co2+ ions (S = 3/2).
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1723, September, 2007. 相似文献
43.
A new nickel(Ⅱ)-dicyanamide compound, [Ni(dca)2(en)]n (1) (dca=dicyanamide anion, [N(CN)2]-); en=ethylene diamine), has been synthesized and its structure has been determined by single crystal X-ray diffraction analysis. The crystal is monoclinic, space group P21/n with unit cell dimensions: a=0.694 3(1) nm, b=1.041 5(2) nm, c=1.4132(2) nm, and β=90.381°, Z=4, V=1.011 0(3) nm3. In this compound, the adjacent nickel atoms are connected by dca all in μ1,5-bridging mode to form ladder-like units, which are linked with double dca bridges to generate a regular infinite stair-like structure. Temperature-dependent magnetic susceptibility was also characterized for this compound. CCDC: 208276. 相似文献
44.
在许多重要的金属蛋白中,都存在ⅡB金属与半胱氨酸残基配位的活性中心M(Cys-S)_n.锌、镉、汞与含硫配体的配位化学作为M(Cys-S)_n中心的化学基础,三配位的[M(SR)_3]被认为是金属蛋白中ⅡB金属的一种配位形式.而近年来,Koch报道了平面三配位的锌、镉、汞的硫酚配合物[(n-Pr)_4N][Zn(SC_6HMe_4-2,3,5,6)_3]和[PPh_4][Cd(SC_6H_2Pr_3~i-2,3,6)_3]及[(n-Pr)_4N][Hg(SC_6H_2Pr_3~i-2,4,6)_3]的晶体结构.他们在实验中由于晶体迅速失去溶剂而未能测定以2,4,6-三异丙基硫酚为配体的锌配合物的晶体结构.最近我们合成了这个配合物,并测定了其晶体结构. 相似文献
45.
合成和表征了一种新的Schiff碱配合物MnL(ClO4)*3H2O(1)(其中L为n(水杨醛)∶n(二乙撑三胺)=1∶1缩合而成的Schiff碱).1与FeSO4*7H2O和K3[Fe(ox)3]*3H2O(ox=oxalate)进一步反应,生成了双金属层状配位聚合物{[MnL][FeⅡFeⅢ(ox)3]*1.5H2O}∞(2).IR和Mssbauer谱测定结果表明,2具有二维层状结构,其阴离子层由[FeⅡFeⅢ(ox)3]-单元构成.变温磁化率(5K~100K)测试结果表明,2中的自旋载体之间存在反铁磁交换作用.5K时的磁滞现象表明2在低温时可能存在铁磁有序,这可能是亚铁磁或自旋倾斜造成的. 相似文献
46.
Hiroshi Harada Kanichi Kamiya Hiroyuki Nasu Jun Matsuoka 《Journal of Sol-Gel Science and Technology》1997,10(3):291-300
The sodium dititanate, Na2O·2TiO2 glass was prepared by the sol-gel method. The structure of the glass, especially local environment of Ti4+ ions was examined using X-ray diffraction and X-ray absorption fine structure (XAFS) analyses, and was compared with that of the melt-derived glass with the same composition. It was found that Ti4+ ions are rather in five-fold coordination state, forming TiO5 pyramids with one doubly bonded Ti=O in the gel-glass, while they were in lower coordination state or four-fold coordination in the melt-derived glass. 相似文献
47.
Bart M. J. M. Suijkerbuijk Dr. Duncan M. Tooke Dr. Anthony L. Spek Prof. Dr. Gerard van Koten Prof. Dr. Robertus J. M. Klein Gebbink Prof. Dr. 《化学:亚洲杂志》2007,2(7):889-903
A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe2, R=Br; 2 Zn: E=NMe2, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and 1H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies. 相似文献
48.
Solid state synthesis and structure of two novel polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4](M?Mo,W)†
Hou Hong-Wei Xin Xin-Quan Yu Kai-Bei Wang Zhe-Min Liu Shi-Xiong Huang Jin-Ling 《中国化学》1996,14(2):123-130
The reaction of [NH4]2[MO2S2], AgI and (n-Bu)4NBr in solid state produced the polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4] (1, M? Mo; 2, M? W) which were structurally determined. The crystals of 1 and 2 are isomorphous, monoclinic, space group P21/c. 1, a = l.6624(2), b=1.6699(3), c=l.7217(2) nm, β=98.29(1)°, V=4.729(1) nm3, Z=2, R=0.040, Rw“0.037; 2, a = 1.6636(3), b = 1.6733(3), c = 1.7190(3) nm, β=98.25(1)°, V=4.736(l) nm3, Z = 2, R = 0.038, Rw = 0.047. The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag2I4]2. and [M6O19]2-. The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster. ion, heteropolymetalate and organic cations, while the latter is only composed of heteropolymetalate and organic cations. 相似文献
49.
Mujie Yang Xiaojun Zhang Jianfu Li Zhiquan Shen 《Journal of polymer science. Part A, Polymer chemistry》1992,30(1):63-69
The study of rare earth coordination catalysts for polymerization of 1-octene has been successfully carried out for the first time. Some features and kinetic behavior of polymerization of 1-octene by Nd(naph)3–AIEt3 catalyst system in tetrachloro-methane are described. The overall polymerization activation energy Ea measured was 74.5 kJ/mol and the rate equation could be expressed as Rp = kp [Nd] [M] (kp = 3.21 × 10?3 L/mol s, at 50°C). The catalytic activity of various rare earth elements in Ln (naph)3 and ligands in NdL3 for the polymerization was compared. A 1-octene oligomer with double bonds was obtained. It is either a white or pale yellow waxy semi-solid. Its number-average molecular weight is about 103 and the molecular weight distribution is less than 2. 相似文献
50.
The new layered ternary compound Nb3GexTe6 (x ? 0.90) was prepared by direct combination of the elements taken in the stoichiometric proportions 3 : 1 : 6, heated at 1 000 °C for 10 days in silica tubes and quenched to room temperature. The phase crystallizes in the orthorhombic symmetry, space group Pnma (#62), with the following single crystal refined parameters: a = 643.18(5) pm, b = 1391.98(11)pm and c = 1 154.07(5) pm, with Z = 4. The structure was refined to an R of 3.4% (Rw = 4.6%), with 1969 independent reflexions and 49 parameters. The structure is based on the close stacking of trigonal prismatic (TP) slabs in the AA/BB mode. The slabs can be seen as built up from face sharing biprisms, which are filled either by one or by two niobium cations situated in the middle of the trigonal prisms. The germanium is located in the middle of the common face of two prisms, leading to a rather unusual anionic square coordination. The refinements showed that this latter cation does not fill completely its square site. No cation was found in the van der Waals gap between the slabs. The mean dGe? Te distance (276.5 pm) is in agreement with GeII cations, while some Te …? Te distances (from 333.84 to 361.65pm) are too short for anions in a simple contact. These bonding distances, already mentionned in some MTe2 compounds, are to be ascribed to charge transfer in the structure, with a partial oxidation state for the tellurium anions. Short Nb? Nb and Nb? Ge distances (292.0 and 281.3 pm, respectively) imply intercationic bonding within the slabs. 相似文献