全文获取类型
收费全文 | 183篇 |
免费 | 16篇 |
专业分类
化学 | 152篇 |
力学 | 1篇 |
数学 | 11篇 |
物理学 | 35篇 |
出版年
2023年 | 2篇 |
2021年 | 1篇 |
2020年 | 1篇 |
2019年 | 2篇 |
2018年 | 2篇 |
2016年 | 3篇 |
2015年 | 8篇 |
2014年 | 9篇 |
2013年 | 8篇 |
2012年 | 13篇 |
2011年 | 16篇 |
2010年 | 7篇 |
2009年 | 4篇 |
2008年 | 14篇 |
2007年 | 13篇 |
2006年 | 16篇 |
2005年 | 9篇 |
2004年 | 11篇 |
2003年 | 11篇 |
2002年 | 9篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有199条查询结果,搜索用时 31 毫秒
191.
Back Cover: Large Zero‐Field Splittings of the Ground Spin State Arising from Antisymmetric Exchange Effects in Heterometallic Triangles (Angew. Chem. Int. Ed. 21/2014)
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)
192.
Miras HN Stone DJ McInnes EJ Raptis RG Baran P Chilas GI Sigalas MP Kabanos TA Cronin L 《Chemical communications (Cambridge, England)》2008,(39):4703-4705
A polyoxomolybdenum/vanadium-sulfite {M(18)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(mu(9)-SO(3))](7-), is reported that exhibits a unique structural motif, arising from the incorporation of five V(V) and two V(IV) ions into a {M(18)} cluster framework templated by SO(3)(2-); this cluster compostion was first identified using cryospray mass spectrometry. 相似文献
193.
Hinchliffe A Mair FS McInnes EJ Pritchard RG Warren JE 《Dalton transactions (Cambridge, England : 2003)》2008,(2):222-233
BCl3 cyclizes diazadiene (2,6-Pr(i)2C6H3NCH)2 1 through a dichloroborated intermediate [(2,6-Pr(i)2C6H3NCHCl)2BCl] to give, in polar aprotic solvents, a spontaneously dehyrochlorinated C-chloro diazaborole 4. In contrast, reaction of AlCl3 with 1 forms only acyclic mono- or di-adducts 5a/b and 6. Alkali metal reductions of gave mixtures of 4 and diazaborole [(2,6-Pr(i)2C6H3NCH)2BCl] 7. Pd(0) reduction cleanly gave diazaborole 7. Reduction of 6 gave a low yield of the closed shell C-C coupled dimer 8 of the putative diazadiene radical anion 1.AlCl2 complex monomer. An alternative synthesis for diazadiene (2,6-Pr(i)2C6H4NCPh)2, 2, is reported. Reduction of 2/BCl3, in which additional phenyl groups on the diazadiene C-2 and C-3 atoms hinder the radical coupling observed in , gave predominantly diazaborole .BCl, (9a) contaminated with .BCl2, (9b) the first such stable radical diazadiene complex of boron. All compounds 2-9 were characterized by X-ray diffraction and NMR spectroscopy. Stable radical was additionally characterized by EPR spectroscopy and density functional computation. 相似文献
194.
Selena J. Lockyer Alessandro Chiesa Grigore A. Timco Eric J. L. McInnes Tom S. Bennett Inigo J. Vitorica-Yrezebal Stefano Carretta Richard E. P. Winpenny 《Chemical science》2021,12(26):9104
The implementation of a quantum computer requires both to protect information from environmental noise and to implement quantum operations efficiently. Achieving this by a fully fault-tolerant platform, in which quantum gates are implemented within quantum-error corrected units, poses stringent requirements on the coherence and control of such hardware. A more feasible architecture could consist of connected memories, that support error-correction by enhancing coherence, and processing units, that ensure fast manipulations. We present here a supramolecular {Cr7Ni}–Cu system which could form the elementary unit of this platform, where the electronic spin 1/2 of {Cr7Ni} provides the processor and the naturally isolated nuclear spin 3/2 of the Cu ion is used to encode a logical unit with embedded quantum error-correction. We demonstrate by realistic simulations that microwave pulses allow us to rapidly implement gates on the processor and to swap information between the processor and the quantum memory. By combining the storage into the Cu nuclear spin with quantum error correction, information can be protected for times much longer than the processor coherence.The implementation of a quantum computer requires protecting of information from noise and the ability to perform quantum gates. We present a molecular architecture providing both these ingredients, via an electronic spin 1/2 processor and a nuclear spin 3/2 memory. 相似文献
195.
Miras HN Sorus M Hawkett J Sells DO McInnes EJ Cronin L 《Journal of the American Chemical Society》2012,134(16):6980-6983
The redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {X(2)M(18)} cluster is reported. Extensive investigations using a range of techniques, including correlated ESI-MS, EPR, and UV-vis as a function of reaction time, showed that six complete oscillations interconverting the capsule species present in solution from {P(2)M(18)} to {V(2)M(18)} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. 相似文献
196.
Shanmugam M Engelhardt LP Larsen FK Luban M McInnes EJ Muryn CA Overgaard J Rentschler E Timco GA Winpenny RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(32):8267-8275
The synthesis, structure, EPR, and magnetic studies of two dodecanuclear heterometallic cyclic clusters are reported. The compounds have the general formula [R(2)NH(2)](2)[Cr(10)Cu(2)F(14)(O(2)CCMe(3))(22)] (R=Me, 1 or iPr, 2). Both structures contain an array of metal centers which describe an approximate "hourglass", with an ammonium cation in the center of each half of the figure. The chromium sites are all six-coordinate, with the two copper sites five-coordinate. The majority of metal-metal edges are bridged by a single fluoride and two pivalate ligands, while two Cr--Cu edges are bridged by a single fluoride and a single pivalate. Magnetic studies show that 1 and 2 exhibit similar (but not identical) behavior, which can be attributed to ten antiferromagnetic and two ferromagnetic exchange interactions around the ring which gives an S=0 ground state. Quantum Monte Carlo calculations have been used to quantify the exchange interactions by successfully simulating the susceptibility for the full temperature range and thus clarifying the distinction between 1 and 2. EPR spectroscopy shows signals due to excited states, and a variable-temperature study has provided an estimate of the energy gap between the first excited state (S=1) and second excited state (S=2) for 1 that is consistent with the value obtained using the QMC method. 相似文献
197.
In collisions of heavy ions at extremely high energies, it is possible for a significant quantity of angular momentum to be deposited into the Quark–Gluon Plasma which is thought to be produced. We develop a simple geometric model of such a system, and show that it is dual, in the AdS/CFT sense, to a rotating AdS black hole with a topologically planar event horizon. However, when this black hole is embedded in string theory, it proves to be unstable, for all non-zero angular momenta, to a certain non-perturbative effect: the familiar planar black hole, as used in most AdS/CFT analyses of QGP physics, is “fragile”. The upshot is that the AdS/CFT duality apparently predicts that the QGP should always become unstable when it is produced in peripheral collisions. However, we argue that holography indicates that relatively low angular momenta delay the development of the instability, so that in practice it may be observable only for peripheral collisions involving favorable impact parameters, generating extremely large angular momenta. In principle, the result may be holographic prediction of a cutoff for the observable angular momenta of the QGP, or perhaps of an analogous phenomenon in condensed matter physics. 相似文献
198.
Wedge CJ Timco GA Spielberg ET George RE Tuna F Rigby S McInnes EJ Winpenny RE Blundell SJ Ardavan A 《Physical review letters》2012,108(10):107204
We show that the electron spin phase memory time, the most important property of a molecular nanomagnet from the perspective of quantum information processing, can be improved dramatically by chemically engineering the molecular structure to optimize the environment of the spin. We vary systematically each structural component of the class of antiferromagnetic Cr(7)Ni rings to identify the sources of decoherence. The optimal structure exhibits a phase memory time exceeding 15 μs. 相似文献
199.
Dr. Tian Luo Dr. Zi Wang Yinlin Chen Dr. Hengzhao Li Mengqi Peng Dr. Floriana Tuna Prof. Eric J. L. McInnes Dr. Sarah J. Day Prof. Jie An Prof. Martin Schröder Prof. Sihai Yang 《Angewandte Chemie (International ed. in English)》2023,62(48):e202306267
Deuterium labelling of organic compounds is an important process in chemistry. We report the first example of photocatalytic dehalogenative deuteration of both arylhalides and alkylhalides (40 substrates) over a metal–organic framework, MFM-300(Cr), using CD3CN as the deuterium source at room temperature. MFM-300(Cr) catalyses high deuterium incorporation and shows excellent tolerance to various functional groups. Synchrotron X-ray powder diffraction reveals the activation of halogenated substrates via confined binding within MFM-300(Cr). In situ electron paramagnetic resonance spectroscopy confirms the formation of carbon-based radicals as intermediates and reveals the reaction pathway. This protocol removes the use of precious-metal catalysts from state-of-the-art processes based upon direct hydrogen isotope exchange and shows high photocatalytic stability, thus enabling multiple catalytic cycles. 相似文献