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排序方式: 共有596条查询结果,搜索用时 265 毫秒
31.
Dr. Jessica Rodriguez Dr. György Szalóki Dr. E. Daiann Sosa Carrizo Dr. Nathalie Saffon-Merceron Dr. Karinne Miqueu Dr. Didier Bourissou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1527-1531
Gold(III) π-complexes have been authenticated recently with alkenes, alkynes, and arenes. The key importance of PdII π-allyl complexes in organometallic chemistry (Tsuji–Trost reaction) prompted us to explore gold(III) π-allyl complexes, which have remained elusive so far. The (P,C)AuIII(allyl) and (methallyl) complexes 3 and 3′ were readily prepared and isolated as thermally and air-stable solids. Spectroscopic and crystallographic analyses combined with detailed DFT calculations support tight quasi-symmetric η3-coordination of the allyl moiety. The π-allyl gold(III) complexes are activated towards nucleophilic additions, as substantiated with β-diketo enolates. 相似文献
32.
Dr. Christina Rest Dr. Divya Susan Philips Torsten Dünnebacke Dr. Papri Sutar Dr. Angel Sampedro Jörn Droste Dr. Vladimir Stepanenko Prof. Dr. Michael Ryan Hansen Dr. Rodrigo Q. Albuquerque Prof. Dr. Gustavo Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(44):10005-10013
Besides their widespread use in coordination chemistry, 2,2’-bipyridines are known for their ability to undergo cis–trans conformational changes in response to metal ions and acids, which has been primarily investigated at the molecular level. However, the exploitation of such conformational switching in self-assembly has remained unexplored. In this work, the use of 2,2’-bipyridines as acid-responsive conformational switches to tune supramolecular polymerization processes has been demonstrated. To achieve this goal, we have designed a bipyridine-based linear bolaamphiphile, 1 , that forms ordered supramolecular polymers in aqueous media through cooperative aromatic and hydrophobic interactions. Interestingly, addition of acid (TFA) induces the monoprotonation of the 2,2’-bipyridine moiety, leading to a switch in the molecular conformation from a linear (trans) to a V-shaped (cis) state. This increase in molecular distortion along with electrostatic repulsions of the positively charged bipyridine-H+ units attenuate the aggregation tendency and induce a transformation from long fibers to shorter thinner fibers. Our findings may contribute to opening up new directions in molecular switches and stimuli-responsive supramolecular materials. 相似文献
33.
Jun TakayamaSeiko Fukuda Yoshiaki SugiharaAkihiko Ishii Juzo Nakayama 《Tetrahedron letters》2003,44(28):5159-5162
Hetero Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide (1) with thioaldehydes and thioketones take place exclusively, except the reaction with thiobenzophenone, at the syn-π-face of 1 with respect to the SO bond. The π-face selectivity was explained in terms of the extent of conformational changes of 1 that are brought about in the process to the transition states. 相似文献
34.
An expedient route to tetracyclo[6.5.2.02,7.09,13]pentadec-2(7),11-dien-14-one and tetracyclic framework of conidiogenol have been reported. Cycloaddition of annulated cyclohexa-2,4-dienone with cyclopentadiene, photochemical oxa-di-π-methane reaction and a highly unusual dehalogenation of bridgehead halogen are the key features of our methodology. 相似文献
35.
36.
Three new lacunar-type derivatives of β-unsubstituted dibenzotetraaza[14]annulene have been synthesized along with a range of their open-chain pendant group containing counterparts. The crystal structures of two representative products have been determined and the noncovalent interactions explored. A number of C-H?π and π?π interactions involving aliphatic chains and aromatic regions of the macrocycle have been evidenced. The relative ease and high yield of lacunization are suggested to be largely due to self-assembly processes, driven by favorable noncovalent interactions between reacting units. 相似文献
37.
Two new hybrid compounds, [Cu(1)(phen)(H2O)][Cu(2)(phen)(H2O)]([Cu(3)]0.25(H2O)][P2Mo5O23]·3.75H2O (1) and [Cu(en)2]1.5[P2Mo5O23]2·(enH2)3·2H2O (2) (phen = 1,10-phenanthroline, en = ethylenediamine), have been hydrothermally synthesized and characterized by IR, UV–Vis spectroscopy, X-ray photoelectron spectroscopy (XPS), powder XRD analyses, TG analyses, cyclic voltammogram analyses, elemental analyses, and single crystal X-ray diffraction analyses. Single crystal X-ray diffraction analyses reveal that the two compounds have a 1-D chain structure formed by Strandberg-type POMs and TMCs with –A–B–C–B–A–B–C–B– linking mode, then further extend into a 2-D layer structure through π?π or hydrogen bond interactions. 相似文献
38.
A new dual chemosensor (TTF-PBA) for Fe3+ and Cu2+ in different signal pathways was designed and synthesized. The absorption spectrum, fluorescence spectrum and cyclic voltammograms changed in the presence of Cu2+ and Fe3+. The optical color changed within 5 s from yellow to orange upon the addition of Cu2+, and it changed to dark yellow when Fe3+ existed. The cyclic voltammogram of Cu2+/TTF-PBA changed from Eox = 0.50 V, Ered = 0.32 V to Eox = 0.64 V, Ered = 0.80 V (vs Ag/AgCl) upon the addition of 2.0 equiv. Cu2+. As for Fe3+/TTF-PBA, its oxidation wave disappeared, and its reduction wave appeared at Ered = ?0.59 V (vs Ag/AgCl) upon the addition of 4.0 equv. Fe3+. The sensor displayed high selectivity for Cu2+ and Fe3+ over other ions including Pb2+, Zn2+, Ni2+, Ag+, Cr3+, Mn2+, Al3+, Co2+, Pd2+, Hg2+, Fe2+, Cd2+, Ce3+, Bi3+ and Au3+, the detection limits for Cu2+ and Fe3+ ion reached as low as 5.33 × 10?7 mol/L and 5.34 × 10?7 mol/L, respectively. Furthermore, when Fe3+ existed, Cu2+ can be detected sequentially by the sensor through the absorption spectrum and the color change observed by naked-eyes. 相似文献
39.
Development of organic semiconductors is one of the most intriguing and productive topics in material science and engineering. Many efforts have been made on the synthesis of aromatic building blocks such as benzene, thiophene and pyrrole due to the facile preparation accompanied by the intrinsic environmental stability and relatively efficient properties of the resulting polymers. In the past, furan has been less explored in this field because of its high oxidation potential. Recently, furan has attracted obsession due to its weaker aromaticity, the greater solubilities of furan-containing π-conjugated polymers relative to other benzenoid systems and the accessibility of furan-based starting materials from renewable resources. This review elaborates the advancements of organic photovoltaic polymers containing furan building blocks. The uniqueness and advantages of furan-containing building blocks in semiconducting materials are also discussed. 相似文献
40.
The push-pull characters of a large series of donor-acceptor substituted azo dyes—71 structures in all—have been quantified by the NN double bond lengths, dNN, the 15N NMR chemical shift differences, Δδ15N, of the two nitrogen atoms and the quotient, π∗/π, of the occupations of the antibonding π∗, and bonding π orbitals of this partial NN double bond. The excellent correlation of the occupation quotients with the bond lengths strongly infers that both π∗/π and dNN are excellent parameters for quantifying charge alternation in the push-pull chromophore and the molecular hyperpolarizability, β0, of these compounds. By this approach, selected compounds can be appropriately considered as viable candidates for nonlinear optical (NLO) applications. 相似文献