全文获取类型
收费全文 | 545篇 |
免费 | 10篇 |
国内免费 | 9篇 |
专业分类
化学 | 376篇 |
晶体学 | 47篇 |
力学 | 3篇 |
数学 | 28篇 |
物理学 | 110篇 |
出版年
2022年 | 2篇 |
2021年 | 6篇 |
2019年 | 5篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 4篇 |
2014年 | 13篇 |
2013年 | 10篇 |
2012年 | 29篇 |
2011年 | 22篇 |
2010年 | 10篇 |
2009年 | 12篇 |
2008年 | 24篇 |
2007年 | 22篇 |
2006年 | 17篇 |
2005年 | 24篇 |
2004年 | 15篇 |
2003年 | 27篇 |
2002年 | 30篇 |
2001年 | 27篇 |
2000年 | 16篇 |
1999年 | 14篇 |
1998年 | 28篇 |
1997年 | 10篇 |
1996年 | 24篇 |
1995年 | 10篇 |
1994年 | 13篇 |
1993年 | 10篇 |
1992年 | 10篇 |
1991年 | 17篇 |
1990年 | 6篇 |
1989年 | 2篇 |
1988年 | 9篇 |
1987年 | 5篇 |
1986年 | 13篇 |
1985年 | 15篇 |
1984年 | 11篇 |
1983年 | 7篇 |
1982年 | 4篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 5篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1971年 | 1篇 |
1967年 | 1篇 |
1966年 | 2篇 |
排序方式: 共有564条查询结果,搜索用时 15 毫秒
21.
The reaction of alkali metal hexacyanoferrate(II/III) with (CH2)6N4 (hexamethylenetetramine, abbreviated HMT) in an acidic medium yielded crystalline compounds of stoichiometries HK2[Fe111(CN)6]·2HMT·4H2O, H2K2[Fe11(CN)6]·2HMT·4H2O, and HNa2[Fe111(CN)6]· 2HMT·5H2O. Their crystal structures are based on a packing of three molecular components: neutral and/orprotonated HMT, hexacyanoferrate, and an alkali metal ion-water cluster. The resulting three-dimensional supramolecular framework is constructed from the coordination of the alkali metal ion by aqua ligands as well as [Fe(CN)6]{n–} and HMT units, and further stabilization is achieved by hydrogen bonding between water molecules and the noncoordinated nitrogen atoms of HMT and hexacyanoferrate. 相似文献
22.
The first successful attempt to construct supramolecular entities via incorporation of bifunctional exodentate ligands into the silver acetylide system is reported. Coordination assembly with nitrogen-donor spacers led to the formation of five distinct supramolecular complexes, namely [(Ag(2)C(2))(AgCF(3)CO(2))(4)(pyz)(2)](n) (1), [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(CF(3)CO(2))(4)(DabcoH)(4)(H(2)O)(1.5)].H(2)O (2), [(Ag(2)C(2))(AgCF(3)CO(2))(4)(CF(3)CO(2))(bpaH)](n)() (3), [(Ag(2)C(2))(AgCF(3)CO(2))(8)(bpa)(4)](n) (4), and [(Ag(2)C(2))(2)(AgCF(3)CO(2))(10)(bppz)(2)(H(2)O)](n) (5) (pyz = pyrazine; Dabco = 1,4-diazabicyclo[2.2.2]octane; bpa = 1,2-bis(4-pyridyl)ethane; bppz = 2,3-bis(2-pyridyl)pyrazine). Complex 1 is a three-dimensional framework composed of silver columns cross-linked by pyrazine bridges, whereas 2 contains a discrete supermolecule whose core is a Ag(14) double cage that is completely surrounded by trifluoroacetate, aqua, and terminal monoprotonated Dabco ligands. Complex 3 has a branched-tree architecture with one terminal of the bpa ligand attached to the silver backbone and the other exposed and protonated. In 4, neutral decanuclear [(Ag(2)C(2))(AgCF(3)CO(2))(8)] units are interlinked by bpa spacers adopting both gauche and anti conformations to generate a layer structure. Another two-dimensional network was formed with bppz serving as an angular bridging ligand in 5, in which the building unit is a silver quadruple cage containing 24 silver atoms. 相似文献
23.
The binuclear cobalt(II) amide complex [(CoL2)2-(TMEDA)] (1) [L = N(Si(t)BuMe2)(2-C5H3N-6-Me); TMEDA = Me2NCH2CH2NMe2] has been synthesized by the reaction of anhydrous CoCl2 with 2 equiv of [Li(L)(TMEDA)]. X-ray crystallography revealed that complex 1 consists of two [CoL2] units linked by one TMEDA ligand molecule, which binds in an unusual N,N'-bridging mode. Protolysis of 1 with the bulky phenol Ar(Me)OH (Ar(Me) = 2,6-(t)Bu2-4-MeC6H2) and thiophenol ArSH (Ar = 2,4,6-(t)Bu3C6H2) gives the neutral monomeric cobalt(II) bis(aryloxide) [Co(OAr(Me))2(TMEDA)] (2) and dithiolate [Co(SAr)2(TMEDA)] (3), respectively. Complexes 1-3 have been characterized by mass spectrometry, microanalysis, magnetic moment, and melting-point measurements, in addition to X-ray crystallography. 相似文献
24.
Crystals of 4(C2H5)4N+F– · 11H2O are orthorhombic, space groupPna21, witha=16.130(3),b=16.949(7),c=17.493(7) Å, andZ=4. The structure was shown to be a clathrate hydrate containing infinite chains of edge-sharing (H2O)4F– tetrahedra extending parallel to thea axis. The chains are laterally linked by bridging water molecules to form a three-dimensional hydrogen-bonded anion/water framework. The ordered (C2H5)4N+ cations occupy the voids in two open channel systems running in theb andc directions. FinalR
F
=0.091 for 2278 observed MoK data measured at 22°C.
Supplementary Data: relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82010 (20 pages).Dedicated to Professor H. M. Powell. 相似文献
25.
Chun-Kiu Kwok Thomas C. W. Mak 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(5):461-471
N,N-DicyclohexylpiperazineN,N-dioxide octahydrate, C16H46N2O10,M
r=426.55, monoclinic, space groupC2/m (No. 12),a=12.961(4),b=11.533(4),c=7.907(1) Å, =98.37(2)o,V=1169.3(6) Å3,Z=2. The structure was solved by the direct method and refined toR=0.045 for 1192 observed MoK
reflections. TheN,N-dioxide molecule occupies a site of symmetry 2/m. The piperazine ring takes the chair form with the two N–O bonds oriented axially in atrans configuration. Hydrogen bonding between the water molecules, as well as between theN-oxide groups and water molecules, gives rise to a puckered layer composed of edge-sharing four-membered, five-membered, six-membered, and eight-membered rings. Adjacent layers are cross-linked by theN,N-dicyclohexylpiperazine moieties lying between them, thereby generating a sandwich structure consolidated by covalent and hydrogen bonding.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82062 (8 pages). 相似文献
26.
27.
Zou Jianzhong Hu Xiaodong Duan Chenying Xu Zheng You Xiaozeng Mak Thomas C. W. 《Transition Metal Chemistry》1998,23(4):477-480
Reaction of either K3[Fe(CN)6] or K4[Fe(CN)6] with a macrocyclic CuII complex, [Cu(teta)](ClO4)2 (teta = 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacylotetradecane), in aqueous solution gave the same product as shown by spectroscopic and physicochemical characterisation. The crystal structure of the complex shows that it is a one-dimensional linear chain type heterobinuclear FeIII–CuII polymer. The unit is composed of a [Cu(teta)(H2O)2]2+ cationic complex, a FeIII–CuII alternate linear chain unit, a ClO
4
–
ion and four water molecules. The Cu atom is coordinated in a distorted octahedral arrangement by four nitrogen atoms from one teta ligand and two nitrogen atoms of the bridging cyanide groups. The Cu—N bond distances involving the cyanide bridges, 2.522(7) and 2.608(7)Å, respectively, indicate weak antiferromagnetic interactions between the FeIII and CuII atoms. 相似文献
28.
George S Nangia A Lam CK Mak TC Nicoud JF 《Chemical communications (Cambridge, England)》2004,(10):1202-1203
Crystalline nitrodiphenyl ureas adopt the N-H...O tape alpha-network only when stabilization accrues from the I...O(2)N or C[triple bond]C-H...O(2)N synthon, otherwise the ureanitro motif is preferred; soft, weak interactions can direct polar self-assembly in strong N-HO hydrogen-bonded crystals. 相似文献
29.
Huatian Shi Jianhui Xie William W. Y. Lam Wai-Lun Man Chi-Keung Mak Shek-Man Yiu Hung Kay Lee Tai-Chu Lau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(56):12895-12899
The synthesis and X-ray structure of a new manganese(V) mesitylimido complex with a tetraamido macrocyclic ligand (TAML), [MnV(TAML)(N-Mes)]− ( 1 ), are reported. Compound 1 is oxidized by [(p-BrC6H4)3N ]+.[SbCl6]− and the resulting MnVI species readily undergoes H-atom transfer and nitrene transfer reactions. 相似文献
30.
Dr. Sam C. K. Hau Prof. Dr. Thomas C. W. Mak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(17):5387-5400
Single‐crystal X‐ray diffraction of a series of ten crystalline silver(I)–trifluoroacetate complexes that contained designed ligands, each of which was composed of an aromatic system that was functionalized with terminal and internal ethynyl groups and a vinyl substituent, provided detailed information on the influence of ligand disposition and orientation, coordination preferences, and the co‐existence of different types of silver(I)–carbon bonding interactions (silver–ethynide, silver–ethynyl, silver–ethenyl, and silver–aromatic) on the construction of coordination networks that were consolidated by argentophilic and weak inter/intramolecular interactions. The complex Ag L10? 6 AgCF3CO2 ? H2O ? MeOH ( HL10 =1‐{[4‐(prop‐2‐ynyloxy)‐3‐vinylphenyl]ethynyl}naphthalene) is the first reported example that exhibits all four kinds of silver(I)–carbon bonding interactions in the solid state. 相似文献