全文获取类型
收费全文 | 3257篇 |
免费 | 496篇 |
国内免费 | 93篇 |
专业分类
化学 | 3443篇 |
晶体学 | 81篇 |
力学 | 9篇 |
综合类 | 6篇 |
数学 | 137篇 |
物理学 | 170篇 |
出版年
2024年 | 5篇 |
2023年 | 36篇 |
2022年 | 42篇 |
2021年 | 83篇 |
2020年 | 142篇 |
2019年 | 97篇 |
2018年 | 95篇 |
2017年 | 68篇 |
2016年 | 187篇 |
2015年 | 154篇 |
2014年 | 202篇 |
2013年 | 255篇 |
2012年 | 226篇 |
2011年 | 180篇 |
2010年 | 158篇 |
2009年 | 200篇 |
2008年 | 238篇 |
2007年 | 266篇 |
2006年 | 202篇 |
2005年 | 218篇 |
2004年 | 200篇 |
2003年 | 110篇 |
2002年 | 54篇 |
2001年 | 48篇 |
2000年 | 54篇 |
1999年 | 60篇 |
1998年 | 50篇 |
1997年 | 47篇 |
1996年 | 42篇 |
1995年 | 37篇 |
1994年 | 18篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 6篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有3846条查询结果,搜索用时 31 毫秒
81.
Vojinović K McLachlan LJ Hinchley SL Rankin DW Mitzel NW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):3033-3042
The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A. 相似文献
82.
《Chemphyschem》2003,4(6):588-594
The reorientational dynamics of the ionic liquid 1butyl‐3‐methylimidazolium hexafluorophosphate ([BMIM]PF6) were studied over a wide range of temperatures by measurement of 13C spin–lattice relaxation rates and NOE factors. The reorientational dynamics were evaluated by performing fits to the experimental relaxation data. Thus, the overall reorientational motion was described by a Cole–Davidson spectral density with a Vogel–Fulcher–Tammann temperature dependence of the correlation times. The reorientational motion of the butyl chain was modelled by a combination of the latter model for the overall motion with a Bloembergen–Purcell–Pound spectral density and an Arrhenius temperature dependence for the internal motion. Except for C2 in the aromatic ring, an additional reduction of the spectral density by the Lipari–Szabo model had to be employed. This reduction is a consequence of fast molecular motions before the rotational diffusion process becomes effective. The C2 atom did not exhibit this reduction, because the librational motion of the corresponding C2? H vector is severely hindered due to hydrogen bonding with the hexafluorophosphate anion. The observed dynamic features of the [BMIM]+ cation confirm quantum‐chemical structures obtained in a former study. 相似文献
83.
Markham George D. Bock Cindy L. Trachtman Mendel Bock Charles W. 《Structural chemistry》1999,10(4):263-276
Ab initio molecular orbital and density functional methods have been used to study the potential energy surfaces of the substituted acetic acids HX—CH2—COOH, where X is one of the Group VIA Chalcophiles S, Se, or Te. The various conformers adopted by these compounds provide information regarding the energetic importance of nonbonded
and
hydrogen bonding interactions involving oxygen atoms with different hybridizations. Density functional and ab initio molecular orbital methods yield similar structural and energetic trends for these compounds. Calculations show that the structure of the lowest-energy conformer of each of these acids has the X—C—C—O backbone substantially twisted from planarity, similar to that previously observed for the corresponding aldehydes, HX—CH2—CHO. In the twisted acid structures the shortest
distance is within about 0.1 Å of the sum of the X and O van der Waals radii, which reduces overcrowding of the lone pairs of electrons on these atoms. In conformers where the heavy atom backbone is planar, one of the
distances is significantly shorter than the sum of the van der Waals radii, and the total molecular energy of these conformers is higher than that of the twisted forms. The variation of X—H vibrational frequencies among conformers reflects the extent of X—H hydrogen bonding, and indicates that formation of this hydrogen bond is not the dominant factor in determining the lowest-energy conformation. When X is oxygen (HO—CH2—COOH), the lowest-energy conformer is also nonplanar, whereas for the corresponding aldehyde, HO—CH2—CHO, the lowest-energy conformer is a planar structure with CS symmetry. The conformational preferences of these simple species provide reference points for inter- and intramolecular interactions in more complex systems of biological interest. 相似文献
84.
一个新的噻二唑衍生物H2ADTZ与锰的二维聚合物的合成与晶体结构(英) 总被引:2,自引:0,他引:2
A new 1,3,4 thiadiazole-derivative ligand 2,5-(s-acetic acid) dimercapto-1,3,4 thiadiazole (H2ADTZ) and its one-dimensional manganese polymer Mn(ADTZ)·4H2O had been synthesized and structurally characterized by X-ray single crystal diffraction in this paper. The Mn(Ⅱ) ion is coordinated with a distorted octahedron by two oxygen atoms from neighboring two deprotonated ligands ADTZ2- and other four oxygen atoms from four coordinated water molecules. The structural feature of the title compound is the formation of one-dimensional manganese chains polymer through the bridging of dioxygen O-O units. In the solid state structure of the complex, one-dimensional manganese chains are joined together by the weak intermolecular hydrogen bonds and vander Waals interactions forming a two-dimensional supramolecular compound. Furthermore, the UV spectra and electro-chemical properties of the title compound were also investigated. CCDC: 260532. 相似文献
85.
CHEN Wen-Tong GUO Guo-Cong ZENG Xi-Rui LI Xin-Fa FANG Xiao-Niu KUANG Han-Mao LIU Dong-Sheng LIU Li-Min 《结构化学》2007,26(10)
The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms. 相似文献
86.
Furusho Y Oku T Hasegawa T Tsuboi A Kihara N Takata T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2895-2903
A dynamic covalent approach to disulfide-containing [2]- and [3]rotaxanes is described. Symmetrical dumbbell-shaped compounds with two secondary ammonium centers and a central located disulfide bond were synthesized as components of rotaxanes. The rotaxanes were synthesized from the dumbbell-shaped compounds and dibenzo-[24]crown-8 (DB24C8) with catalysis by benzenethiol. The yields of isolated rotaxanes reached about 90 % under optimized conditions. A kinetic study on the reaction forming [2]rotaxane 2 a and [3]rotaxane 3 a suggested a plausible reaction mechanism comprising several steps, including 1) initiation, 2) [2]rotaxane formation, and 3) [3]rotaxane formation. The whole reaction was found to be reversible in the presence of thiols, and thermodynamic control over product distribution was thus possible by varying the temperature, solvent, initial ratio of substrates, and concentration. The steric bulk of the end-capping groups had almost no influence on rotaxane yields, but the structure of the thiol was crucial for reaction rates. Amines and phosphines were also effective as catalysts. The structural characterization of the rotaxanes included an X-ray crystallographic study on [3]rotaxane 3 a. 相似文献
87.
Constantinos M. Paleos Dimitris Tsiourvas 《Angewandte Chemie (International ed. in English)》1995,34(16):1696-1711
The role of hydrogen bonding in the formation or stabilization of liquid crystalline phases has only recently been appreciated. Following the first, wellestablished examples of liquid crystal formation from the dimerization of aromatic carboxylic acids, through hydrogen bonding, several classes of compounds have recently been synthesized, the liquid crystalline behavior of which is also dependent on intermolecular hydrogen bonds between similar or dissimilar molecules. In this review the main classes of compounds exhibiting liquid crystallinity due to hydrogen bonding are presented to show the diversity of organic compounds that can be used as building elements in liquid crystals. The molecules are either of the rigid-rod anisotropic or amphiphilic types such as molecules appropriately functionalized with pyridyl and carboxyl groups, whose interaction leads to the formation of liquid crystals; amphiphilic carbohydrates and amphiphilic and bolaamphiphilic compounds with multiple hydroxyl groups whose dimerization or association is indispensable for the formation of liquid crystals; and certain amphiphilic carboxylic acids with monomeric or polymeric mesogens and amphiphilic-type compounds bearing different moieties, whose interaction may lead to the formation of mesomorphic compounds. Associated with the macroscopic display of liquid crystalline phases is the supramolecular structure, and therefore rather extended discussion of these structures are included in this review. 相似文献
88.
Jin-long Wu Zhen-ya Zeng Lan-hua Wei Ling-zhi Meng Ting-xian Yang 《Tetrahedron》2004,60(19):4309-4314
Three new neutral receptors (1, 2 and 3) containing thiourea and amide groups were synthesized by simple steps in good yields. The binding properties for anions of 1, 2 and 3 were examined by UV-vis, fluorescence, and 1H NMR spectroscopy. Receptors 1, 2 and 3 all had a better adipate anion selectivity by comparison with other dicarboxylate anions. The association constants of 1, 2 and 3 with adipate were higher as compared to other anions (malonate, succinate, glutarate). In particular, a distinct color change was observed from light yellow to orange-red upon addition of adipate to the solution of 1 in DMSO. The UV-vis and fluorescence data indicate that a 1:1 stoichiometry complex is formed between compound 1, 2 or 3 and dicarboxylate anions through hydrogen bonding interactions. 相似文献
89.
Erik Rakovský Ľudmila Žúrková Jaromír Marek 《Monatshefte für Chemie / Chemical Monthly》2002,133(3):277-283
Summary. Anhydrous 1,6-hexanediammonium dihydrogendecavanadate ((HdaH2)2H2V10O28, 1) was prepared by reaction of V2O5 with 1,6-hexanediamine in aqueous solution. The crystal structure of 1 was determined, and the proton positions in the H2V10O28
4− anion were calculated by the bond length/bond number method. The protons are bound to the centrosymmetrically oriented μ–OV3 groups of the decavanadate anion. Based on the analysis of IR spectra of 1 prepared from H2O and D2O, the absorption band at 871 cm−1 can be attributed to δ(V–Ob–H) vibrations.
Received August 3, 2001. Accepted (revised) October 8, 2001 相似文献
90.
New organohalogermanes RGe(OCH2CH2NMe2)2X (R = Ph, X = I (5); R = Me, X = Cl (6) or I (7)) with an intramolecular N→Ge coordination bond were synthesized. According
to the 1H and 13C NMR spectroscopic data, iodides 5 and 7 exist in solution as ionic compounds with the pentacoordinated germanium atom. In
solution of compound 4 (R = Ph, X = Cl), there is an equilibrium between the ionic and covalent forms. The equilibrium shifts
toward the ionic form with increasing solvent polarity or temperature. In solution, chloride 6 is a covalent compound. The
structures and relative stabilities of different isomers of compounds 4–7 were studied by quantum chemical calculations at
the density functional level of theory.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 892–900, May, 2007. 相似文献