全文获取类型
收费全文 | 204篇 |
免费 | 9篇 |
专业分类
化学 | 167篇 |
晶体学 | 10篇 |
数学 | 12篇 |
物理学 | 24篇 |
出版年
2020年 | 2篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 7篇 |
2014年 | 6篇 |
2013年 | 8篇 |
2012年 | 11篇 |
2011年 | 8篇 |
2010年 | 8篇 |
2009年 | 14篇 |
2008年 | 11篇 |
2007年 | 8篇 |
2006年 | 7篇 |
2005年 | 11篇 |
2004年 | 7篇 |
2003年 | 9篇 |
2002年 | 14篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1978年 | 2篇 |
1977年 | 5篇 |
1975年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有213条查询结果,搜索用时 15 毫秒
1.
2.
Krahl T Stösser R Kemnitz E Scholz G Feist M Silly G Buzaré JY 《Inorganic chemistry》2003,42(20):6474-6483
The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction. 相似文献
3.
4.
Ignat'eva DV Goryunkov AA Tamm NB Ioffe IN Avdoshenko SM Sidorov LN Dimitrov A Kemnitz E Troyanov SI 《Chemical communications (Cambridge, England)》2006,(16):1778-1780
Two isomers of C70(CF3)12 have been isolated from a mixture obtained by trifluoromethylation of C70 with CF3I; their molecular structures determined by X-ray crystallography are in good agreement with the results of theoretical DFT calculations for the most stable C70(CF3)12 isomers. 相似文献
5.
O. Böse E. Kemnitz A. Lippitz W. E. S. Unger 《Analytical and bioanalytical chemistry》1997,358(1-2):175-179
A number of partially catalytically active aluminium compounds characterised by powder XRD have been investigated by XPS and
XAES using a new method for static charge referencing [1, 2]. In detail, α-Al2O3, γ-Al2O3, boehmite γ-AlO(OH), bayerite α-Al(OH)3, hydrargillite γ-Al(OH)3, α-AlF3, β-AlF3, and AlF2.3(OH)0.7· H2O and a hexa-fluoropropylene oxide (HFPO) modified γ-Al2O3 are examined. Well defined and chemically inert 20 nm gold particles are deposited as a nearly statistical distribution on
the sample surface avoiding large coagulation effects. This procedure allows a determination of gold referenced XPS and XAES
data sets. Binding energies (BE) of Al 2p, Al 2s, O 1s and F 1s photoelectron peaks as well as kinetic energies (KE) of Al
KLL and F KLL Auger electron emission peaks are presented in relation to the Au 4f7/2 BE reference. XPS and XAES data found in literature are, in most cases, C 1s referenced and scatter in a broad range. BE
differences Δ between the C 1s charge reference BE and Au 4f7/2 charge reference BE obtained with our samples are monitored by using the Al 2p orbital. These BE differences Δ clearly suggest
that the chemical state of carbon observed in this study is not as uniform as required for reliable static charge referencing.
Received: 24 June 1996 / Revised: 12 December 1996 / Accepted: 14 December 1996 相似文献
6.
Structures of Chlorinated Fullerenes,IPR C96Cl20 and Non‐classical C94Cl28 and C92Cl32: Evidence of the Existence of Three New Isomers of C96 下载免费PDF全文
Prof. Dr. Shangfeng Yang Tao Wei Song Wang Dr. Ilya N. Ioffe Prof. Dr. Erhard Kemnitz Prof. Dr. Sergey I. Troyanov 《化学:亚洲杂志》2014,9(11):3102-3105
Chlorination of various HPLC fractions of C96 with a mixture of VCl4 and SbCl5 at 340–360 °C and single‐crystal X‐ray diffraction study of the products led to the identification of three new IPR isomers of C96. The C96(175) isomer forms a stable chloride, C96(175)Cl20, while chlorides of two other new isomers, C96(114) and C96(80), undergo cage shrinkage yielding C94(NC1)Cl28 and C96(NC2)Cl32 with non‐classical (NC) cages. These two NC chlorides contain, respectively, one and two heptagons flanked by pairs of fused pentagons and are stabilized by chlorine attachment to the emerging pentagon–pentagon junctions. Thus, the number of the experimentally confirmed C96 isomers has reached nine, which corroborates the empirical rule that the C6n fullerenes exhibit particularly rich isomerism. 相似文献
7.
Carl R. Kemnitz Prof. Joel L. Mackey Mark J. Loewen Julie L. Hargrove Joshua L. Lewis Whitney E. Hawkins Adam F. Nielsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6942-6949
The potential origins of stability in branched alkanes are investigated, paying close attention to two recent hypotheses: geminal steric repulsion and protobranching. All alkane isomers through C6H14 along with heptane and octane were investigated at the MPW1B95/6‐311++G(d,p) level. Their geminal steric repulsion, total steric repulsion, and orbital interactions were evaluated by using natural bond orbital analysis. All measures of steric repulsion fail to explain the stability of branched alkanes. The extra stability of branched alkanes and protobranching, in general, is tied to stabilizing geminal σ→σ* delocalization, particularly of the type that involves adjacent C? C bonds and, thus, preferentially stabilizes branched alkanes. This picture is corroborated by valence bond calculations that attribute the effect to additional ionic structures (e.g., CH3+ :CH2 :CH3? and CH3:? CH2: CH3+ for propane) that are not possible without protobranching. 相似文献
8.
Single crystals of (NMe4)(HF2) were obtained during attempted recrystallization of NMe4F from fluoroolefin. X‐ray diffraction data show that (NMe4)(HF2) crystallizes in the orthorhombic space group Pmmn with unit cell dimensions a = 6.535(2), b = 8.688(3), and c = 5.333(2) Å. The symmetric and virtually linear HF2 anions exhibit a short F···F distance of 2.256(2) Å. The both crystal structures of (NMe4)(H2F3) (orthorhombic, Pbca, a = 8.509(1), b = 11.273(2), and c = 14.880(2) Å) and CsH2F3 (orthorhombic, P212121, a = 7.345(3), b = 9.126(4), and c = 11.444(4) Å) contain dihydrogentrifluoride anions, H2F3?, which have a bent shape and F···F distances of 2.30‐2.34Å. 相似文献
9.
10.
Natalia A. Romanova Maria A. Fritz Dr. Kaichin Chang Dr. Nadezhda B. Tamm Dr. Alexey A. Goryunkov Prof. Lev N. Sidorov Dr. Chuanbao Chen Prof. Shangfeng Yang Prof. Erhard Kemnitz Prof. Sergey I. Troyanov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11707-11716
Trifluoromethylation of a higher fullerene mixture with CF3I was performed in ampoules at 550 °C. HPLC separation followed by crystal growth and X‐ray diffraction study resulted in the structure elucidation of nine CF3 derivatives of D2d‐C84 (isomer 23). The molecular structures of C84(23)(CF3)4, C84(23)(CF3)8, C84(23)(CF3)10, C84(23)(CF3)12, two isomers of C84(23)(CF3)14, two isomers of C84(23)(CF3)16, and C84(23)(CF3)18 were discussed in terms of their addition patterns and the relative formation energies. Extensive theoretical DFT calculations were performed to identify the most stable molecular structures. It was found that the addition of CF3 groups to the C84(23) fullerene is governed by two main rules: no additions in positions of triple hexagon junctions and predominantly para additions in C6(CF3)2 hexagons on the fullerene cage. The only exception with an isolated CF3 group in C84(23)(CF3)12 is discussed in more detail. 相似文献