全文获取类型
收费全文 | 4673篇 |
免费 | 608篇 |
国内免费 | 1110篇 |
专业分类
化学 | 5721篇 |
晶体学 | 127篇 |
力学 | 12篇 |
综合类 | 32篇 |
数学 | 311篇 |
物理学 | 188篇 |
出版年
2024年 | 14篇 |
2023年 | 63篇 |
2022年 | 148篇 |
2021年 | 214篇 |
2020年 | 275篇 |
2019年 | 267篇 |
2018年 | 177篇 |
2017年 | 207篇 |
2016年 | 278篇 |
2015年 | 272篇 |
2014年 | 338篇 |
2013年 | 486篇 |
2012年 | 329篇 |
2011年 | 281篇 |
2010年 | 243篇 |
2009年 | 283篇 |
2008年 | 305篇 |
2007年 | 324篇 |
2006年 | 283篇 |
2005年 | 249篇 |
2004年 | 227篇 |
2003年 | 195篇 |
2002年 | 152篇 |
2001年 | 96篇 |
2000年 | 95篇 |
1999年 | 71篇 |
1998年 | 54篇 |
1997年 | 64篇 |
1996年 | 55篇 |
1995年 | 71篇 |
1994年 | 51篇 |
1993年 | 30篇 |
1992年 | 50篇 |
1991年 | 37篇 |
1990年 | 27篇 |
1989年 | 27篇 |
1988年 | 13篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有6391条查询结果,搜索用时 15 毫秒
151.
Jin Hong 《Journal of Molecular Structure》2003,655(3):435-441
X-ray crystallographic analysis and density functional B3LYP/6-31G(d) calculation confirm that dimeric water is embedded within a hydrophobic cavity of tetra-(p-tert-butyl)thiacalix[4]arene and stabilized by hydrogen bondings of aromatic π?H2O(1) and methyl?H2O(2) in the dimeric water inclusion complex with binding energies of 1.4 and 0.9 kcal mol−1 respectively, and by hydrogen bonding formed between H2O(2) and four phenolic OH groups from an adjacent tetra-(p-tert-butyl)thiacalix[4]arene, with binding energy of 3.8-4.2 kcal mol−1. 相似文献
152.
Takeharu Haino 《Tetrahedron letters》2005,46(9):1411-1414
C60-linked calix[5]arenes were synthesized and their intramolecular binding properties were investigated. The self-inclusion ratio of the C60 moiety was determined by using UV-vis spectroscopy, and the ratio depends on chain length, temperature, and solvent. Influence of temperature and solvent was explained by the thermodynamic data of the intramolecular complex formation process. 相似文献
153.
Maria Atanassova Victoria Lachkova Nikolay Vassilev Sabi Varbanov Ivan Dukov 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):173-179
The synergistic solvent extraction of five selected lanthanoid ions (La3+, Nd3+, Eu3+, Ho3+ and Lu3+) with a 4-benzoyl-3-methyl-1-phenyl-5-pyrazolone(HP) and the 5,11,17,23-tert-butyl-25,26,27,28-tetrakis(dimethylphosphinoylmethoxy)calix[4]arene, (S) in CHCl3 has been studied. It was found that in presence of this phosphorus-containing calix[4]arene the lanthanoids have been extracted
as LnP3 · S. On the basis of the experimental data, the values of the equilibrium constants have been calculated. The influence of
the synergistic agent on the extraction process has been discussed. A synergistic effect of almost three orders of magnitude
occurs in the extraction of Ln(III) with mixture of HP and S. The values of the separation factors (S.F.) between the adjacent
elements have been evaluated.
On the basis of the IR and NMR spectra the stoichiometry and the structure of the solid complexes of Eu(III) with HP and Eu(III)
with HP and S were proposed. 相似文献
154.
Qian-Feng Zhang Richard D. Adams Dieter Fenske 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(3):275-279
The self-assemblies of two pyrogallol[4]arenes held together by 48 intermolecular hydrogen bonds stably associate in the form of spherical hexameric capsules. The molecular structures of two hexameric capsules with large interior space were analyzed by single crystal X-ray crystallography. 相似文献
155.
Reaction of COC12.6H20 with equimolar bis(3,5-dimethylpyrazolyl)methane (dmpzm) produced a mononuclear adduct [Co(dmpzm)Cl2] (1). Treatment of 1 with sodium dicyanamide (dca) afforded a polymeric complex [Co(dmpzm)(μ-dca)2]∞ (2). 1 and 2 were characterized by elemental analysis, IR spectra, thermogravimetric analysis and single-crystal X-ray diffraction. The cobalt atom in 1 adopts a distorted tetrahedral coordination geometry, bound to two N atoms of one dmpzm and two Cl atoms. Complex 2 has a 2D brick-wall network (extended along the bc plane) in which the { [Co(dmpzm)(μ-dca)]2} n^2n+ chains are interconnected by pairs of μ-dca anions along the c axis. The magnetic properties of 1 and 2 were also investigated. 相似文献
156.
A new class of M(II)–Hg(II) (M=Cu(II), Co(II), Ni(II)) mixed-metal coordination polymers, Cu(2-pyrazinecarboxylate)2HgCl2 (4), [Co(2-pyrazinecarboxylate)2(HgCl2)2] · 0.61H2O (5) and [Ni(2-pyrazinecarboxylate)2(HgCl2)2] · 0.77H2O (6), have been prepared by self assembly of metal-containing building blocks, M(2-pyrazinecarboxylate)2 · (H2O)2(M=Cu(II), Co(II), Ni(II)), with HgCl2. Compounds 4–6 were characterized fully by IR, elemental analysis and single crystal X-ray diffraction. Compound 4 crystallized in the monoclinic space group C2/c, with a=17.916(5) Å, b=7.223(2) Å, c=13.335(4) Å, β=128.726(3)°, V=1346.2(6) Å3, Z=4. It contains alternating Hg(II) and Cu(II) metal centers that are cross-linked by 2-pyrazinecarboxylate spacers and chlorine co-ligands to generate a unique three-dimensional Hg(II)–Cu(II) mixed metal framework. Compound 5 crystallized in the triclinic space group P
, with a=6.3879(7) Å, b=6.6626(8) Å, c=13.2286(15) Å, α=96.339(2)°, β=91.590(2)°, γ=113.462(2)°, V=511.71(10) Å3, Z=1. Compound 6 also crystallized in the triclinic space group P
, with a=6.3543(8) Å, b=6.6194(8) Å, c=13.2801(16) Å, α=96.449(2)°, β=92.263(2)°, γ=113.541(2)°, V=506.67(11) Å3, Z=1. Compounds 5 and 6 are isostructural and in the solid state the Hg(II)M(II)Hg(II) units are connected by Hg2Cl2 linkages to produce a novel M(II)–Hg(II) (M=Co(II), Ni(II)) zigzag mixed-metal chain, in which a new type of M–M′–M′–M array was observed. The metal containing building blocks, M(2-pyrazinecarboxylate)2 · (H2O)2 (M=Cu(II), Co(II), Ni(II)), exhibit different connectivities to HgCl2 depending on the metal cation contained within them. 相似文献
157.
N(1)取代5-氟尿嘧啶乙酸、5-氟尿嘧啶丙酸与Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)的配合物的合成及表征 总被引:1,自引:0,他引:1
合成了N(1)取代5-氟尿嘧啶乙酸、5-氟尿嘧啶丙酸与铜(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)和锰(Ⅱ)的十种金属配合物。通过元素分析、差热-热重分析确定了它们的化学组成,并对这些化合物进行了红外光谱、氢核磁共振谱,电子光谱的表征。讨论了各配合物中金属离子与配体的配位状态。在Cu(Ⅱ)配合物中,Cu(Ⅱ)是与配体的N3原子和C4上的羰基氧原子配位,其他金属配合物中,金属离子是与配体的C2的羰基氧原子和羧基配位。 相似文献
158.
芳香二磺酸的配位化学研究化合物[Ni(cyclam)(1,5nds)]·1/3H_2O(1)和[Co(cyclam)(H_2O)_2](1,5nds)·2H_2O(2)的合成与结构(英文)
下载免费PDF全文
![点击此处可从《无机化学学报》网站下载免费的PDF全文](/ch/ext_images/free.gif)
合成了两个二价的过渡金属磺酸化合物,并通过X-射线衍射单晶结构分析进行结构表征。化合物犤Ni(cyclam)(1,5nds)犦·1/3H2O(1)以P2(1)/c空间群结晶,晶胞参数为a=8.583(5),b=10.533(6),c=12.946(7)?,β=92.433(9)°。犤Ni(cyclam)犦2+与两个磺酸基团形成弱配位,从而构筑了一维的配聚物。犤Ni(cyclam)犦2+与磺酸基团之间的作用还通过O2S-O…H-N型氢键进一步被加强。化合物犤Co(cyclam)(H2O)2犦(1,5nds)·2H2O(2)以P1珔空间群结晶,晶胞参数为a=8.738(5),b=9.324(5),c=10.118(5)?,α=81.382(8),β=64.868(8),γ=62.999(8)°。在该化合物中,磺酸基团没有与Co2+形成配位键,而是以平衡离子的形式存在并与配离子形成氢键,构筑了有序的三维结构。 相似文献
159.
Ki Cheol Song 《Tetrahedron letters》2007,48(31):5397-5400
A new chemosensor with a phenanthroimidazole subunit based upon calix[4]arene-diamide has been synthesized, and its Mg2+-selective fluoroionophoric properties were investigated in an aqueous DMSO solution. The compound exhibited a pronounced Mg2+-selective fluoroionophoric behavior over other physiologically relevant metal ions. A significant red shift in fluorescence emission (Δλ = 86 nm) provided the ratiometric determination as well as naked-eye detection of Mg2+ ions. 相似文献
160.
Olivier SénèqueOlivia Reinaud 《Tetrahedron》2003,59(29):5563-5568
Eight novel calix[6]arene-based biomimetic ligands for transition metal ions have been synthesized. They display a non-symmetrical N3, N4 or N3ArO binding core that mimics enzyme active sites presenting histidine and tyrosine residues. The key step for their synthesis is the mono-alkylation at the small rim of the C3v symmetrical trimethyl ether derivative of tBu-calix[6]arene with N-Boc-2-chloroethylamine to yield a novel calix[6]arene synthon. Its combined O-alkylation with a chloromethyl aromatic amine and N-deprotection or alkylation or reductive alkylation with a salicylaldehyde derivative yielded the calix[6]arene-based ligands with mixed N/O donors. 相似文献