全文获取类型
收费全文 | 119篇 |
免费 | 12篇 |
专业分类
化学 | 115篇 |
晶体学 | 4篇 |
数学 | 5篇 |
物理学 | 7篇 |
出版年
2021年 | 1篇 |
2020年 | 1篇 |
2019年 | 1篇 |
2016年 | 2篇 |
2015年 | 6篇 |
2014年 | 8篇 |
2013年 | 3篇 |
2012年 | 8篇 |
2011年 | 10篇 |
2010年 | 4篇 |
2009年 | 5篇 |
2008年 | 2篇 |
2007年 | 7篇 |
2006年 | 4篇 |
2005年 | 3篇 |
2004年 | 12篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 6篇 |
2000年 | 18篇 |
1999年 | 6篇 |
1998年 | 1篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1987年 | 2篇 |
1899年 | 1篇 |
排序方式: 共有131条查询结果,搜索用时 312 毫秒
111.
Ohne Zusammenfassung 相似文献
112.
A New Conformation With an Extraordinarily Long, 3.04 Å Two‐Electron,Six‐Center Bond Observed for the π‐[TCNE]22− Dimer in [NMe4]2[TCNE]2 (TCNE=Tetracyanoethylene)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Adora G. Graham Dr. Fernando Mota Dr. Endrit Shurdha Prof. Arnold L. Rheingold Prof. Juan J. Novoa Prof. Joel S. Miller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(38):13240-13245
[NMe4]2[TCNE]2 (TCNE=tetracyanoethenide) formed from the reaction of TCNE and (NMe4)CN in MeCN has νCN IR absorptions at 2195, 2191, 2172, and 2156 cm?1 and a νCC absorption at 1383 cm?1 that are characteristic of reduced TCNE. The TCNEs have an average central C?C distance of 1.423 Å that is also characteristic of reduced TCNE. The reduced TCNE forms a previously unknown non‐eclipsed, centrosymmetric π‐[TCNE]22? dimer with nominal C2 symmetry, 12 sub van der Waals interatomic contacts <3.3 Å, a central intradimer separation of 3.039(3) Å, and comparable intradimer C???N distances of 3.050(3) and 2.984(3) Å. The two pairs of central C???C atoms form a ?C?C???C?C of 112.6° that is substantially greater than the 0° observed for the eclipsed D2h π‐[TCNE]22? dimer possessing a two‐electron, four‐center (2e?/4c) bond with two C???C components from a molecular orbital (MO) analysis. A MO study combining CAS(2,2)/MRMP2/cc‐pVTZ and atoms‐in‐molecules (AIM) calculations indicates that the non‐eclipsed, C2 π‐[TCNE]22? dimer exhibits a new type of a long, intradimer bond involving one strong C???C and two weak C???N components, that is, a 2e?/6c bond. The C2 π‐[TCNE]22? conformer has a singlet, diamagnetic ground state with a thermally populated triplet excited state with J/kB=1000 K (700 cm?1; 86.8 meV; 2.00 kcal mol?1; H=?2 JSa?Sb); at the CAS(2,2)/MBMP2 level the triplet is computed to be 9.0 kcal mol?1 higher in energy than the closed‐shell singlet ground state. The results from CAS(2,2)/NEVPT2/cc‐pVTZ calculations indicate that the C2 and D2h conformers have two different local metastable minima with the C2 conformer being 1.3 kcal mol?1 less stable. The different natures of the C2 and D2h conformers are also noted from the results of valence bond (VB) qualitative diagram that shows a 10e?/6c bond with one C???C and two C???N bonding components for the C2 conformer as compared to the 6e?/4c bond for the D2h conformer with two C???C bonding components. 相似文献
113.
114.
Catala L Le Moigne J Gruber N Novoa JJ Rabu P Belorizky E Turek P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2440-2454
The present work completes and extends our previous reports on the determination of the magnetic ground state and on the strength of the through bond exchange coupling within series of biradicals. This knowledge was subsequently exploited for the analysis of the magnetic interactions in their crystals. We report here the studies of series of triradicals incorporating alpha-nitronyl nitroxides (NN) or alpha-imino nitroxides (IN) as terminal radical fragments connected through a m-phenylene coupling unit in one case and a phenyl acetylene unit in other case. Tetraradical derivatives have also been studied. The studies of isolated molecules (EPR in solution and DFT calculations) allow the assessment of the magnetic interactions through the magnetic coupling unit. All triradical derivatives are found to exhibit a quartet ground state, whereas a singlet ground state is determined for the tetraradical. This last result reinforces previous findings that the singlet ground state is favoured in related biradicals involving similar m-phenylene couplers. Moreover, the through bond magnetic exchange coupling for the ortho-meta connectivity could be demonstrated as being ferromagnetic, thus ascertaining our previous hypotheses. The magnetic properties of the triradicals and tetraradicals in their solid state have been rationalized by using a previously proposed methodology, allowing to identify the most relevant magnetic pathways. 相似文献
115.
Several 6-phenyl-3(2H)-pyridazinones bearing different alkenyl groups at position 5 have been prepared in the search for novel antiplatelet agents. The target compounds were synthesised by a palladium-catalysed Heck cross-coupling reaction. Variable amounts of 4-phenyl-6-substituted-2-phthalazinones were isolated as by-products during these experiments. The crucial issues for successful Heck coupling in these systems concern the protection of position 2 of the heterocyclic ring and the use of tris(o-tolyl)phosphine as a ligand. 相似文献
116.
Minguet M Amabilino DB Cirujeda J Wurst K Mata I Molins E Novoa JJ Veciana J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(13):2350-2361
An extensive investigation of the conformations adopted by the family of phenyl alpha-nitronyl nitroxides has been carried out. A database containing 110 crystal structures was used in a statistical study of the solid-state geometries and conformations of these radicals. This study revealed that the favoured conformations involve a twisted distortion in the imidazolyl rings and a twist between the aromatic and heterocyclic rings in the molecules. As a consequence, these radicals show two types of preferred conformations in the solid state: the pseudo-anti enantiomeric pair and the pseudo-eclipsed pair, the latter type being the most statistically probable. A new chiral member of this group of radicals that bears a lactate moiety, (R)-1, and its corresponding racemic compound, (R,S)-1, have been prepared in order to study the influence of chiral induction from the stereogenic centre on the torsion angle between the aromatic and heterocyclic rings of the alpha-nitronyl nitroxides. The X-ray crystal structures of the enantiopure and racemic compounds, which both reveal chains of molecules sustained by strong O-H...O hydrogen bonds between the carboxylic acid group and the ON group of the radical in the solid, as well as their magnetic properties have been determined. Remarkably, the molecules with a given stereogenic centre have a single helical sense between their component rings, even in the racemic crystal. Chiral induction from the stereogenic centre to the radical unit has also been proved by CD spectroscopy in the solid state. The results of these experiments have been rationalised by ab initio calculations of the spectra. 相似文献
117.
M. Carme Rovira Juan J. Novoa Myung-Hwan Whangbo Jack M. Williams 《Chemical physics》1995,200(3):319-335
On the basis of ab initio MP2/6–31 + + G(2d,2p) calculations, we examined the potential energy surfaces of the water·hydrocarbon complexes H2O·CH4, H2O·C2H2 and H2O·C2H2 to locate all the minimum energy structures and estimate the hydrogen bond energies and vibrational frequencies associated with the C(spn)---H·O and the O---H·C(spn) bonds (n = 1−3). Our calculations show that H2O·C2H2, H2O·C2H4 and H2O·CH4 have two minimum energy structures (i.e., the C---H·O and O---H·C hydrogen bond forms), but H2O·C2H4 has only one when the vibrational motion is taken into account, the O---H·C hydrogen bond form. We have also computed the barrier for the interconversion from one minimum to the other. The fully optimized geometries of H2O·CH4, H2O·C2H4 and H2O·C2H2 as well as the vibrational shifts of the C---H stretching frequencies in their C---H·O hydrogen-bonded forms are in good agreement with the available experimental data. The calculated hydrogen bond energies show that the C(spn---H·O bond strengths decrease in the order C(sp)---H·O>C(sp2)---H·O>C(sp3)---O>C(sp3---H·O, which is also consistent with the available experimental data. 相似文献
118.
Lam BM Halfen JA Young VG Hagadorn JR Holland PL Lledós A Cucurull-Sánchez L Novoa JJ Alvarez S Tolman WB 《Inorganic chemistry》2000,39(18):4059-4072
With the goal of understanding how the nature of the tridentate macrocyclic supporting ligand influences the relative stability of isomeric mu-eta 2:eta 2-peroxo- and bis(mu-oxo)dicopper complexes, a comparative study was undertaken of the O2 reactivity of Cu(I) compounds supported by the 10- and 12-membered macrocycles, 1,4,7-R3-1,4,7-triazacyclodecane (R3TACD; R = Me, Bn, iPr) and 1,5,9-triisopropyl-1,5,9-triazacyclododecane (iPr3TACDD). While the 3-coordinate complex [(iPr3TACDD)Cu]SbF6 was unreactive with O2, oxygenation of [(R3TACD)Cu(CH3CN)]X (R = Me or Bn; X = ClO4- or SbF6-) at -80 degrees C yielded bis(mu-oxo) species [(R3TACD)2Cu2(mu O)2]X2 as revealed by UV-vis and resonance Raman spectroscopy. Interestingly, unlike the previously reported system supported by 1,4,7-triisopropyl-1,4,7-triazacyclononane (iPr3TACN), which yielded interconverting mixtures of peroxo and bis(mu-oxo) compounds (Cahoy, J.; Holland, P. L.; Tolman, W. B. Inorg. Chem. 1999, 38, 2161), low-temperature oxygenation of [(iPr3TACD)Cu(CH3CN)]SbF6 in a variety of solvents cleanly yielded a mu-eta 2:eta 2-peroxo product, with no trace of the bis(mu-oxo) isomer. The peroxo complex was characterized by UV-vis and resonance Raman spectroscopy, as well as an X-ray crystal structure (albeit of marginal quality due to disorder problems). Intramolecular attack at the alpha C-H bonds of the substituents was indicated as the primary decomposition pathway of the oxygenated compounds through examination of the decay kinetics and the reaction products, which included bis(mu-hydroxo)- and mu-carbonato-dicopper complexes that were characterized by X-ray diffraction. A rationale for the varying results of the oxygenation reactions was provided by analysis of (a) the X-ray crystal structures and electrochemical behavior of the Cu(I) precursors and (b) the results of theoretical calculations of the complete oxygenated complexes, including all ligand atoms, using combined quantum chemical/molecular mechanics (integrated molecular orbital molecular mechanics, IMOMM) methods. The size of the ligand substituents was shown to be a key factor in controlling the relative stabilities of the peroxo and bis(mu-oxo) forms, and the nature of this influence was shown by both theory and experiment to depend on the ligand macrocycle ring size. 相似文献
119.
120.
Joaquim Jornet-Somoza Mercè Deumal Mark M. Turnbull Juan J. Novoa 《Polyhedron》2009,28(9-10):1965-1971
The First-Principles Bottom–Up study of the 88 K and 273 K X-ray diffraction structures of the bis-2,3-dimethylpyridinium tetrabromocuprate molecular magnet shows that the analysis of the magnetic properties of a molecule-based magnet, that does not present any first order polymorphic transition in the range of temperature studied, depends on the X-ray structure employed. The reason is the thermal expansion anisotropy when the crystal goes from the low temperature phase to 273 K, which induces changes in the radical–radical JAB interactions. As a consequence, the magnetic topology of the low temperature and 273 K structures change, a fact that induces a change in the macroscopic magnetic susceptibility curve (only the 88 K structure of bis-2,3-dimethylpyridinium tetrabromocuprate reproduces well the two-leg spin ladder experimental properties of this magnet). When anisotropic thermal effects are suspected one should use low temperature structures to study the magnetic properties at low temperature, and high temperature structures for the study of the magnetic properties in that range of temperatures. 相似文献