全文获取类型
收费全文 | 3853篇 |
免费 | 431篇 |
国内免费 | 739篇 |
专业分类
化学 | 4745篇 |
晶体学 | 98篇 |
力学 | 2篇 |
综合类 | 10篇 |
数学 | 1篇 |
物理学 | 167篇 |
出版年
2024年 | 4篇 |
2023年 | 27篇 |
2022年 | 108篇 |
2021年 | 157篇 |
2020年 | 223篇 |
2019年 | 174篇 |
2018年 | 145篇 |
2017年 | 145篇 |
2016年 | 223篇 |
2015年 | 188篇 |
2014年 | 222篇 |
2013年 | 320篇 |
2012年 | 457篇 |
2011年 | 245篇 |
2010年 | 215篇 |
2009年 | 235篇 |
2008年 | 244篇 |
2007年 | 246篇 |
2006年 | 215篇 |
2005年 | 182篇 |
2004年 | 231篇 |
2003年 | 158篇 |
2002年 | 91篇 |
2001年 | 76篇 |
2000年 | 65篇 |
1999年 | 84篇 |
1998年 | 51篇 |
1997年 | 47篇 |
1996年 | 37篇 |
1995年 | 30篇 |
1994年 | 27篇 |
1993年 | 23篇 |
1992年 | 30篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 6篇 |
1988年 | 19篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有5023条查询结果,搜索用时 31 毫秒
101.
102.
Alenka Turi?nik 《Journal of fluorine chemistry》2003,121(2):245-251
[Mg(HF)2](SbF6)2 and [Ca(HF)2](SbF6)2 monocrystals were grown from the corresponding hexafluoroantimonates(V) dissolved in anhydrous hydrogen fluoride. [Mg(HF)2](SbF6)2 crystallizes in the space group Pnma (no. 62) with a=1249.1(4) pm, b=1230.2(4) pm, c=699.1(2) pm, V=1.0742(6) nm3, Z=4. Magnesium is octahedrally coordinated by six fluorine atoms from which two belong to two HF molecules. The structure can be represented by alternating rows of magnesium and antimony atoms running parallel to the c-axis. Magnesium atoms are connected by cis bridging Sb(2)F6 units along the a-axis and by trans bridging Sb(1)F6 units along the b-axis. In this way a three-dimensional network is formed.[Ca(HF)2](SbF6)2 crystallizes in the space group P21/n (no. 14) with a=935.2(3) pm, b=1088.7(3) pm, c=1104.8(3) pm, β=106.697(5)°, V=1.0774(5) nm3, Z=4. The coordination sphere around the calcium atom consists of eight fluorine atoms which define the vertices of an Archimedean antiprism. The two HF molecules directly coordinate the calcium atom and their fluorine atoms are placed in the corners of different square faces of the Archimedean antiprism. The Ca-F(HF) distances are shorter than the Ca-F(Sb) distances. The Sb(1)F6 and Sb(2)F6 groups have four equatorial bridging fluorine atoms, while the Sb(3)F6 groups have only two bridging trans F ligands. The Ca atoms in the [−1,0,1] plane are connected by equatorial F ligands of Sb(1)F6 and Sb(2)F6 units, forming a [Ca(SbF6)+]n layer. These layers are connected by trans bridging Sb(3)F6 groups. HF molecules occupy the space between these layers and additionally contribute to the connection between the layers by hydrogen bonding. 相似文献
103.
Smaragda Grammenudi Marlene Franke Fritz Vögtle Eberhard Steckhan 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):695-707
The tris-bipyridine ligand3a and its stoichiometric Rh3+ complex have been prepared. Cyclovoltammograms of the complex at pH 7.4 using a glassy carbon disk electrode reveal a strong reduction peak at –620 mV and two weak reduction peaks at more negative voltage. The reduction potential of the new complex is shifted by 300 mV to more positive values as compared to [Rh(bipy)3]3+. There is no reversible reoxidation peak of the Rh(I) complex formed due to the decomplexation of one of the three bipyridine units in the course of the transition Rh(III)Rh(I). The Rh(III) complex of3a was also studied with respect to its function as a possible redox mediator for the electrochemical regeneration of NADH from NAD+. The preparative electrolysis of the Rh3+ complex of3a in the presence of NAD+ yields a selective formation of NADH, whereas NAD dimers were not detected. On the other hand, a significant acceleration of this reaction compared to [Rh(bipy)3]3+ was not observed. 相似文献
104.
Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition
metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities
for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex
catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition,
several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and
Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic
behavior with size-selective molecular recognition. 相似文献
105.
Menozzi E Busi M Ramingo R Campagnolo M Geremia S Dalcanale E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(10):3136-3148
The self-assembly of open ditopic and tetratopic cavitand complexes has been investigated by using monofunctionalized cavitand ligands and suitable metal precursors. In the case of ditopic complexes, self-assembly protocols, leading exclusively to the formation of both thermodynamically stable cis-Pt square-planar complexes 8 and 9 and the kinetically inert fac-Re octahedral complex 14, have been elaborated. The use of cis-[Pt(CH3)CN)2Cl2] as metal precursor led to the formation of monotopic trans-10 and ditopic trans-11 cavitand complexes, while cis-[Pt(dmso)2Cl2] afforded both cis-13 and trans-11 isomers. The self-assembly of tetratopic cavitand complexes has been achieved by using mononuclear [Pd(CH3CN)4(BF4)2] and dinuclear [M2(tppb)(OTf)4] (19: M = Pt; 20: M = Pd) metal precursors. Only the tetratopic dinuclear complexes 21 and 22 were stable. The ligand configuration with two phosphorus and two cavitand ligands at the metal centers is the most appropriate to build tetratopic cavitand complexes with sufficient kinetic stability. 相似文献
106.
Preparation and characterization of Mg(II)-, Ca(II) and Cd(II) complexes of 1,2-ethanediol and water
Mixed ligand complexes of different compositions were prepared with water, sulfate ion and 1,2-ethanediol as ligand. IR spectra and the thermoanalytical curves of the complexes were recorded. Oxygen atoms bound by one or two coordinate bonds to the metal ion, or by hydrogen-bonds in the crystal, were observed. As for the water molecule, 1,2-ethanediol molecules of crystal and monohydrate type were found, depending on the type of binding of the oxygen atoms.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
107.
A new method for the synthesis of azo Schiff an base ligand in which the azo and azomethine groups are coordination sites was developed through a Schiff base precursor. The precursor, N-4-methoxybenzylidene-3-hydroxyphenylamine (SB) derived from 3-aminophenol was regioselectively coupled with a diazonium ion para to the hydroxyl group of the amine component of the Schiff base. The para selectivity was controlled by the directing effect of the hydroxyl group. The ligand and its nickel(Ⅱ) complex were characterized by elemental analyses, IR and UV-Vis spectroscopy. The analytical and spectral data supported the mononuclear formulation of the complex with metal to ligand ratio (M : L = 1 : 2) and suggested a square planar geometry for the complex. 相似文献
108.
通过酸洗、硅烷偶联剂表面活化、键合苯甲酰异硫氰酸酯对蒙脱土进行改性,制得新型固相萃取(SPE)材料。 采用红外光谱、扫描电子显微镜、X射线光电子能谱表征了改性蒙脱土的结构和形貌。 考察了制备的SPE填料对水中As3+、Bi3+、Cu2+、Sb3+、Sn2+和Pb2+的吸附性能,确定了最佳固相萃取条件,对6种金属离子吸附容量分别为10.83、11.92、12.67、10.43、10.01及10.54 mg/g。 通过SPE与电感耦合等离子体质谱联用测定了样品中As3+、Bi3+、Cu2+、Sb3+、Sn2+和Pb2+ 6种重金属离子的含量,检出限分别为0.024、0.013、0.075、0.037、0.011和0.064 μg/L。 相似文献
109.
Two cobalt(II) coordination polymers formed from bte (bte = 1,2-bis(1,2,4-triazol-1-yl)ethane), namely [Co(bte)2(dca)2]n (1) and {[Co(bte)(dca)2] · H2O}n (2), have been synthesized and characterized by elementary analyses, IR, thermogravimetric analyses, X-ray diffraction analyses and magnetic measurements. Compound 1 is a double-chain with Co(II) centers bridged by bte, containing metallocycles of [Co2(bte)2] and trans dca as termination ligands. In 2, each Co(II) center is bonded by two bridging bte ligands and four dca as μ-1,5-dca in different orientations in the 3D network. 相似文献
110.