全文获取类型
收费全文 | 614篇 |
免费 | 99篇 |
国内免费 | 31篇 |
专业分类
化学 | 710篇 |
晶体学 | 7篇 |
物理学 | 27篇 |
出版年
2024年 | 1篇 |
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 13篇 |
2019年 | 33篇 |
2018年 | 26篇 |
2017年 | 16篇 |
2016年 | 26篇 |
2015年 | 27篇 |
2014年 | 45篇 |
2013年 | 58篇 |
2012年 | 39篇 |
2011年 | 43篇 |
2010年 | 32篇 |
2009年 | 29篇 |
2008年 | 33篇 |
2007年 | 35篇 |
2006年 | 49篇 |
2005年 | 43篇 |
2004年 | 47篇 |
2003年 | 30篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 12篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 6篇 |
1996年 | 10篇 |
1995年 | 11篇 |
1994年 | 5篇 |
1993年 | 10篇 |
1992年 | 5篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
排序方式: 共有744条查询结果,搜索用时 31 毫秒
131.
Geometry of an Isolated Dimer of Imidazole Characterised by Rotational Spectroscopy and Ab Initio Calculations
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
John C. Mullaney Dr. Daniel P. Zaleski Dr. David P. Tew Dr. Nicholas R. Walker Prof.Dr. Anthony C. Legon 《Chemphyschem》2016,17(8):1154-1158
An isolated, gas‐phase dimer of imidazole is generated through laser vaporisation of a solid rod containing a 1:1 mixture of imidazole and copper in the presence of an argon buffer gas undergoing supersonic expansion. The complex is characterised through broadband rotational spectroscopy and is shown to have a twisted, hydrogen‐bonded geometry. Calculations at the CCSD(T)(F12*)/cc‐pVDZ‐F12 level of theory confirm this to be the lowest‐energy conformer of the imidazole dimer. The distance between the respective centres of mass of the imidazole monomer subunits is determined to be 5.2751(1) Å, and the twist angle γ describing rotation of one monomer with respect to the other about a line connecting the centres of mass of the monomers is determined to be 87.9(4)°. Four out of six intermolecular parameters in the model geometry are precisely determined from the experimental rotational constants and are consistent with results calculated ab initio. 相似文献
132.
A convenient and efficient TfOH-catalyzed head-to-tail dimerization of vinylarenes has been realized under mild conditions. The present protocol provides an attractive approach to a diverse range of higher olefins in good to excellent yields. 相似文献
133.
Yun-Chang Zhang Lan Chen Hui Wang Ya-Ming Zhou Dan-Wei Zhang Zhan-Ting Li 《中国化学快报》2016,27(6):817-821
Two naphthalene(NP) and bipyridinium(BIPY~(2+)) alternately incorporated polymers P1 and P2 have been prepared through the formation of dynamic hydrazone bonds. The polymers formed NP–BIPY~(2+)donor–acceptor interaction-induced pleated secondary structure. Upon reducing the BIPY~(2+)units to radical cation BIPY+, intramolecular dimerization of the BIPY+units induced the backbones to afford another pleated secondary structure. Adding electron-rich macrocyclic polyether bis-1,5-dinaphtho[38]crown-10 or electron-deficient cyclobis(paraquat-p-phenylene) cyclophane did not break the first foldamer by complexing the BIPY2+or NP units of the polymers, whereas the di(radical cationic)ring of the second cyclophane could break the second foldamer by forming threading complexes with the BIPY+units of the polymers. 相似文献
134.
Bin Liu Takuya Yoshida Prof. Xiaofang Li Prof. Marcin Stępień Prof. Hiroshi Shinokubo Prof. Piotr J. Chmielewski 《Angewandte Chemie (International ed. in English)》2016,55(42):13142-13146
Reversible homolytic dissociation of the bis(pyrimidinenorcorrole) σ‐dimer was elucidated by means of variable temperature ESR and 1H NMR spectroscopy, mass spectrometry, and optical spectrocopy. Dehydrogenation of the σ‐dimer yielded another dimer displaying a singlet–triplet equilibrium in solution, strong NIR absorption (1570 nm), and a narrow electrochemical HOMO–LUMO gap (0.74 V). 相似文献
135.
Isolation and Crystallographic Characterization of the Labile Isomer of Y@C82 Cocrystallized with Ni(OEP): Unprecedented Dimerization of Pristine Metallofullerenes
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Lipiao Bao Changwang Pan Prof. Zdenek Slanina Prof. Filip Uhlik Prof. Takeshi Akasaka Prof. Xing Lu 《Angewandte Chemie (International ed. in English)》2016,55(32):9234-9238
Although the major isomers of M@C82 (namely M@C2v(9)‐C82, where M is a trivalent rare‐earth metal) have been intensively investigated, the lability of the minor isomers has meant that they have been little studied. Herein, the first isolation and crystallographic characterization of the minor Y@C82 isomer, unambiguously assigned as Y@Cs(6)‐C82 by cocrystallization with Ni(octaethylporphyrin), is reported. Unexpectedly, a regioselective dimerization is observed in the crystalline state of Y@Cs(6)‐C82. In sharp contrast, no dimerization occurs for the major isomer Y@C2v(9)‐C82 under the same conditions, indicating a cage‐symmetry‐induced dimerization process. Further experimental and theoretical results disclose that the regioselective dimer formation is a consequence of the localization of high spin density on a special cage‐carbon atom of Y@Cs(6)‐C82 which is caused by the steady displacement of the Y atom inside the Cs(6)‐C82 cage. 相似文献
136.
137.
Ritch JS Chivers T Eisler DJ Tuononen HM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(16):4643-4653
A synthetic protocol for the tert-butyl-substituted dichalcogenoimidodiphosphinates [Na(tmeda){(EPtBu(2))(2)N}] (3 a, E=S; 3 b, E=Se; 3 c, E=Te) has been developed. The one-electron oxidation of the sodium complexes [Na(tmeda){(EPR(2))(2)N}] with iodine produces a series of neutral dimers (EPR(2)NPR(2)E--)(2) (4 b, E=Se, R=iPr; 4 c, E=Te, R=iPr; 5 a, E=S, R=tBu; 5 b, E=Se, R=tBu; 5 c, E=Te, R=tBu). Attempts to prepare 4 a (E=S, R=iPr) in a similar manner produced a mixture including HN(SPiPr(2)). Compounds 4 b, 4 c and 5 a-c were characterised by multinuclear NMR spectra and by X-ray crystallography, which revealed two alternative structures for these dimeric molecules. The derivatives 4 b, 4 c, 5 a and 5 b exhibit acyclic structures with a central chalcogen-chalcogen linkage that is elongated by approximately 2 % (E=S), 6 % (E=Se) and 8 % (E=Te) compared to typical single-bond values. By contrast, 5 c adopts an unique spirocyclic contact ion-pair structure in which a [(TePtBu(2))(2)N](-) ion is Te,Te' chelated to an incipient [(TePtBu(2))(2)N](+) cyclic ion. DFT calculations of the relative energies of the two structural isomers indicate a trend towards increasing stability for the contact ion pair relative to the corresponding dichalcogenide on going from S to Se to Te for both the isopropyl and tert-butyl series. The two-electron oxidation of [Na(tmeda){(EPtBu(2))(2)N}] (E=S, Se, Te) with iodine produced the salts [(EPtBu(2))(2)N](+)X(-) (7 a, E=S, X=I(3); 7 b, E=Se, X=I; 7 c, E=Te, X=I), which were characterised by X-ray crystallography. Compound 7 a exists as a monomeric, ion-separated complex with [d(S--S)=2.084(2) A]; 7 b and 7 c are dimeric [d(Se--Se)=2.502(1) A; d(Te--Te)=2.884(1) A]. 相似文献
138.
研究了β-氯化萘汞在[CIRh(CO)2]2催化下于六甲基磷酰胺溶液中的偶联反应动力学,证明其反应为二级,求得了偶联反应动力学常数.α-氯化萘汞和α-溴汞代苯乙酸乙酯在相同的反应条件下不发生偶联反应;在α一溴汞代苯乙酸乙酯的偶联反应条件下分离和鉴定了有机铑(I)中间体,根据所提出的反应机理,对上述现象进行了讨论. 相似文献
139.
本文报道了p(N,N-二甲氨基)肉桂酸乙酯(DMAC)在十二酸(LA)聚集体中的光谱和光化学性质。这种肉桂酸衍生物的吸收和发射光谱表现出典型的分子内电荷转移的特征,在十二酸存在下,观察到DMAC激基缔合物荧光,荧光强度随DMAC浓度增加而增加,与普通溶液中的反应相比,十二酸聚集体中的DMAC具有较大的光二聚反应速度。用荧光光谱跟踪反应的结果表明,DMAC激基缔合物具有较DMAC单体更高的光化学活性。 相似文献
140.
Yoshinao Nakagawa Nobuo Tajima Kimihiko Hirao 《Journal of computational chemistry》2000,21(14):1292-1304
The hydration reaction of ethylene, C2H4+H2O → C2H5OH, catalyzed by oxoacids (H3PO4, H2SO4, and HClO4) and metal cations (B3+, Al3+, Sc3+, Ga3+, La3+, Be2+, Mg2+, Ca2+, Zn2+, and Sr2+) are studied systematically by density functional theory with a BLYP functional. The reaction profiles of the main reaction and some side reactions, such as ester formation, dimerization of ethylene, and dehydrogenation of ethanol, have been determined with a variety of catalysts. In each case, the intermediate states, the transition states, and their energetics are calculated. Metal cations react more efficiently for the main reaction than oxoacids, but they also make the dehydrogenation reaction active. While the dimerization reaction is strongly affected by the acidity of the catalyst, both the acidity and basicity of the catalyst are important for the dehydrogenation reaction. Efficient formation of ethanol from ethylene over a catalyst is suggested. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1292–1304, 2000 相似文献