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51.
Coordination Complexes of a Neutral 1,2,4‐Benzotriazinyl Radical Ligand: Synthesis,Molecular and Electronic Structures,and Magnetic Properties 下载免费PDF全文
Dr. Ian S. Morgan Akseli Mansikkamäki Georgia A. Zissimou Dr. Panayiotis A. Koutentis Mathieu Rouzières Dr. Rodolphe Clérac Dr. Heikki M. Tuononen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15843-15853
A series of d‐block metal complexes of the recently reported coordinating neutral radical ligand 1‐phenyl‐3‐(pyrid‐2‐yl)‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl ( 1 ) was synthesized. The investigated systems contain the benzotriazinyl radical 1 coordinated to a divalent metal cation, MnII, FeII, CoII, or NiII, with 1,1,1,5,5,5‐hexafluoroacetylacetonato (hfac) as the auxiliary ligand of choice. The synthesized complexes were fully characterized by single‐crystal X‐ray diffraction, magnetic susceptibility measurements, and electronic structure calculations. The complexes [Mn( 1 )(hfac)2] and [Fe( 1 )(hfac)2] displayed antiferromagnetic coupling between the unpaired electrons of the ligand and the metal cation, whereas the interaction was found to be ferromagnetic in the analogous NiII complex [Ni( 1 )(hfac)2]. The magnetic properties of the complex [Co( 1 )(hfac)2] were difficult to interpret owing to significant spin–orbit coupling inherent to octahedral high‐spin CoII metal ion. As a whole, the reported data clearly demonstrated the favorable coordinating properties of the radical 1 , which, together with its stability and structural tunability, make it an excellent new building block for establishing more complex metal–radical architectures with interesting magnetic properties. 相似文献
52.
The Reaction of Bunsen's Cacodyl Disulfide,Me2As(S)‐S‐AsMe2, with Iodine: Preparation and Properties of Dimethylarsinosulfenyl Iodide,Me2As‐S‐I 下载免费PDF全文
Panayiotis V. Ioannou Dimitris G. Vachliotis Athanassios Chrissanthopoulos 《无机化学与普通化学杂志》2015,641(7):1340-1346
Bunsen's cacodyl disulfide, Me2As(S)‐S‐AsMe2 ( 1 ), reacted with iodine giving the novel dimethylarsinosulfenyl iodide, Me2As‐S‐I ( 3 ) although theoretical calculations indicated that the AsV compound Me2As(S)‐I ( 4 ) was more stable in the gas phase. The oily product was stable neat and as a solution in CDCl3 at +4 °C and –20 °C for at least 15 d. Light, H2O, H2O2, and Zn dust, but not NaI or Ag, decomposed it. Compound 3 did not interact with Ph3N, with Ph2NH and PhNH2 it interacted but not reacted. 3 was decomposed by piperidine, with pyridine and 4‐dimethylaminopyridine it interacted and produced Me2As‐SS‐AsMe2 ( 2 ) and I2 that formed charge transfer complexes Base · I2, whereas Et3N decomposed 3 , and 3Et3N · 2I2 was isolated. 3 was desulfurized by Ph3P and (Me2N)3P completely, and by (PhO)3P and (PhS)3P partially. The reactions of 3 with (Me2N)3P, (PhS)3P, and (EtO)3P were complicated. From the AsIII nucleophiles, only Ph3As was bound, while (PhS)3As reacted slowly in a complicated manner with 3 . No interaction of 3 with MeOH or PhOH was observed but NaOH, Ag2O, and PhONa decomposed it. Thiophenol produced traces of Me2As‐SPh ( 10 ) and sodium thiophenolate attacked mainly at AsIII of 3 . Thus, externally stabilized sulfenium ions of the type Me2As‐S‐Nu+I– were not obtained. 相似文献
53.
Silver(I) fluoride (AgF)-mediated intramolecular nonoxidative and oxidative palladium-catalyzed cyclizations of 1,3-diphenyl- and 8-iodo-1,3-diphenylbenzo[e][1,2,4]triazin-7(1H)-ones 6a (R = H) and 7a (R = I) afford a new 'alkaloid like' ring system 2-phenyl-6H-[1,2,4]triazino[5,6,1-jk]carbazol-6-one 8a (triazafluoranthenone) in 86 and 100% yields, respectively. Furthermore, these cyclization protocols were used to prepare triazafluoranthenone analogues 8b-e bearing dialkylamino, methoxy, and phenylsulfanyl substituents at C-5, which were also independently synthesized from triazafluoranthenone 8a by regioselective nucleophilic addition. Similar AgF-mediated intramolecular nonoxidative and oxidative palladium-catalyzed cyclizations of 8,10-dihydro-1-iodo-10-phenylphenazin-2(7H)-ones 13 gave the new 'alkaloid like' ring system 8H-indolo[1,2,3-mn]phenazin-8-one 14 in 80 and 18% yields, respectively. 相似文献
54.
1,3-Diphenylbenzo[e][1,2,4]triazin-7(1H)-one (6) reacts with tetracyanoethylene (TCNE) or tetracyanoethylene oxide (TCNEO) to give the deep green 2-[1,3-diphenylbenzo[e][1,2,4]triazin-7(1H)-ylidene]propanedinitrile (11) in 17 and 15% yields, respectively. Nucleophiles such as amines, alkoxides, thiols and Grignard reagents all reacted with the 1,3-diphenylbenzotriazinone 6 regioselectively at C-6, while halogenating agents reacted exclusively at C-8. Furthermore, 8-iodo-1,3-diphenylbenzo[e][1,2,4]triazin-7(1H)-one (32) undergoes palladium-catalysed Suzuki-Miyaura and Stille coupling reactions to give 8-aryl- or heteroaryl-substituted benzotriazinones. By combining both the C-6 and C-8 chemistries 1,3,6,8-tetraphenylbenzo[e][1,2,4]triazin-7(1H)-one (42) and 1,3-diphenyl-6,8-di(thien-2-yl)-benzo[e][1,2,4]triazin-7(1H)-one (43) can be prepared. All new compounds are fully characterized. 相似文献
55.
Excited-state properties, although extremely useful, are hardly accessible. One indirect way would be to derive them from relationships to ground-state properties which are usually more readily available. Herewith, we present quantitative correlations between triplet excited-state (T?) properties (bond dissociation energy, D?(T?), homolytic activation energy, E(a)(T?), and rate constant, k(r)) and the ground-state bond dissociation energy (D?), taking as an example the photodissociation of the C-Si bond of simple substituted allylsilanes CH?=CHC(R1R2)-SiH? (R1 and R2 = H, Me, and Et). By applying the complete-active-space self-consistent field CASSCF(6,6) and CASPT2(6,6) quantum chemical methodologies, we have found that the consecutive introduction of Me/Et groups has little effect on the geometry and energy of the T? state; however, it reduces the magnitudes of D?, D?(T?) and E(a)(T?). Moreover, these energetic parameters have been plotted giving good linear correlations: D?(T?) = α? + β? · D?, E(a)(T?) = α? + β? · D?(T?), and E(a)(T?) = α? + β? · D? (α and β being constants), while k(r) correlates very well to E(a)(T?). The key factor behind these useful correlations is the validity of the Evans-Polanyi-Semenov relation (second equation) and its extended form (third equation) applied for excited systems. Additionally, the unexpectedly high values obtained for E(a)(T?) demonstrate a new application of the principle of nonperfect synchronization (PNS) in excited-state chemistry issues. 相似文献
56.
Panayiotis Gialamas Benjamin Völker Rachel R. Collino Matthew R. Begley Robert M. McMeeking 《International Journal of Solids and Structures》2014
An analytical model is provided for the peeling of a tape from a surface to which it adheres through cohesive tractions. The tape is considered to be a membrane without bending stiffness and is initially attached everywhere to a flat rigid surface. The tape is assumed to deform in plane strain, and finite deformations in the form of elastic strains are accounted for. The cohesive tractions are taken to be uniform when the tape is within a critical interaction distance from the substrate and then to fall immediately to zero once this critical interaction distance is exceeded. When the distance between the tape and the substrate is zero, repulsive and attractive tractions balance to zero; in this segment, sliding of the tape relative to the substrate is forbidden when we pull the tape up somewhere in the middle, though we permit such sliding when the tape is peeled from one end. In the cohesive zone and where the tape is detached, the interaction of the tape with the substrate is frictionless. Results are given for the force to peel a neo-Hookean tape at any angle up to vertical when one end of it is pulled away from the substrate, as well as for scenarios when the tape is lifted somewhere in the middle to form a V shape being pulled away from the substrate. 相似文献
57.
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59.
Applied Biochemistry and Biotechnology - ASaccharomyces cerevisiae xylulokinase mutant was constructed by using the cloned yeast xylulokinase gene, XYK-Sc, and the gene disruption technique. TheS.... 相似文献
60.
In this article, we study a compression of normal matrices and matrix polynomials with respect to a given vector and its orthogonal complement. The numerical range of this compression satisfies special boundary properties, which are investigated in detail. The characteristic polynomial of the compression is also considered. 相似文献