全文获取类型
收费全文 | 2025篇 |
免费 | 109篇 |
国内免费 | 5篇 |
专业分类
化学 | 1341篇 |
晶体学 | 9篇 |
力学 | 70篇 |
数学 | 149篇 |
物理学 | 570篇 |
出版年
2024年 | 5篇 |
2023年 | 39篇 |
2022年 | 37篇 |
2021年 | 73篇 |
2020年 | 75篇 |
2019年 | 64篇 |
2018年 | 56篇 |
2017年 | 51篇 |
2016年 | 104篇 |
2015年 | 53篇 |
2014年 | 99篇 |
2013年 | 132篇 |
2012年 | 132篇 |
2011年 | 168篇 |
2010年 | 111篇 |
2009年 | 90篇 |
2008年 | 136篇 |
2007年 | 91篇 |
2006年 | 76篇 |
2005年 | 87篇 |
2004年 | 46篇 |
2003年 | 41篇 |
2002年 | 28篇 |
2001年 | 18篇 |
2000年 | 17篇 |
1999年 | 23篇 |
1998年 | 8篇 |
1997年 | 13篇 |
1996年 | 15篇 |
1995年 | 12篇 |
1994年 | 14篇 |
1993年 | 18篇 |
1992年 | 11篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 13篇 |
1984年 | 16篇 |
1983年 | 13篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1977年 | 10篇 |
1976年 | 13篇 |
1975年 | 5篇 |
1974年 | 7篇 |
排序方式: 共有2139条查询结果,搜索用时 15 毫秒
81.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes
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)
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献
82.
One‐Step Multicomponent Self‐Assembly of a First‐Generation Sierpiński Triangle: From Fractal Design to Chemical Reality
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)
Rajarshi Sarkar Kai Guo Dr. Charles N. Moorefield Prof. Mary Jane Saunders Prof. Chrys Wesdemiotis Prof. George R. Newkome 《Angewandte Chemie (International ed. in English)》2014,53(45):12182-12185
A novel terpyridine‐based architecture that mimics a first‐generation Sierpiński triangle has been synthesized by multicomponent assembly and features tpy? CdII? tpy connectivity (tpy=terpyridine). The key terpyridine ligands were synthesized by the Suzuki cross‐coupling reaction. Mixing two different terpyridine‐based ligands and CdII in a precise stoichiometric ratio (1:1:3) produced the desired fractal architecture in near‐quantitative yield. Characterization was accomplished by NMR spectroscopy, mass spectrometry, and transmission electron microscopy. 相似文献
83.
Souvik Sarkar Aritra Sarkar Prof. Dr. Subi J. George 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20013-20017
Stereoselective and temporally controlled supramolecular polymerizations are ubiquitous in nature and are desirable attributes for the design of chiral, well-defined functional materials. Kinetically controlled, living supramolecular polymerization (LSP) has emerged recently for the synthesis of supramolecular polymers with controlled length and narrow dispersity. On the other hand, stringent design requirements for chiral-discriminating monomers precludes the stereoselective control of the supramolecular polymer structure. Herein, a synergetic stereo- and structural control of supramolecular polymerization by the realization of an unprecedented stereoselective seed-induced LSP is reported. Homochiral and seeded growth is demonstrated with bischromophoric naphthalene diimide (NDI) enantiomers with a chiral binaphthyl amine core, exhibiting strong self-recognition abilities and pathway complexity. 相似文献
84.
Sharma Abhishek K. Agrahari Gaurav Tiwari C. B. Tomar B. S. Yelgaonkar V. N. 《Journal of Radioanalytical and Nuclear Chemistry》2020,324(1):143-147
Journal of Radioanalytical and Nuclear Chemistry - In the traditional medicine of Iran, some herbal medicines are used for treating of high blood sugar. In this study, the concentration of Ca, Cr,... 相似文献
85.
Dr. Sebastian Sobottka Maite Nößler Dr. Andrew L. Ostericher Dr. Gunter Hermann Noah Z. Subat Julia Beerhues Dr. Margarethe Behr-van der Meer Dr. Lisa Suntrup Dr. Uta Albold Dr. Stephan Hohloch Dr. Jean Christophe Tremblay Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1314-1327
Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q2−)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q2−=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2−)] with Q2−=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands. 相似文献
86.
Steffen M. Brülls Dr. Valentina Cantatore Zhenping Wang Dr. Pui Lam Tam Dr. Per Malmberg Jessica Stubbe Prof. Dr. Biprajit Sarkar Prof. Dr. Itai Panas Prof. Dr. Jerker Mårtensson Prof. Dr. Siegfried Eigler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6694-6702
Hybridizing graphene and molecules possess a high potential for developing materials for new applications. However, new methods to characterize such hybrids must be developed. Herein, the wet-chemical non-covalent functionalization of graphene with cationic π-systems is presented and the interaction between graphene and the molecules is characterized in detail. A series of tricationic benzimidazolium salts with various steric demand and counterions was synthesized, characterized and used for the fabrication of graphene hybrids. Subsequently, the doping effects were studied. The molecules are adsorbed onto graphene and studied by Raman spectroscopy, XPS as well as ToF-SIMS. The charged π-systems show a p-doping effect on the underlying graphene. Consequently, the tricationic molecules are reduced through a partial electron transfer process from graphene, a process which is accompanied by the loss of counterions. DFT calculations support this hypothesis and the strong p-doping could be confirmed in fabricated monolayer graphene/hybrid FET devices. The results are the basis to develop sensor applications, which are based on analyte/molecule interactions and effects on doping. 相似文献
87.
88.
89.
Venkata Reddy Regalla RamaKrishnam Raju Addada Venkat Swami Puli Abhishek S. Saxena Anindita Chatterjee 《Tetrahedron letters》2017,58(24):2344-2346
A short and efficient method for the stereoselective synthesis of Dendrodolide L has been developed from inexpensive and commercially available starting material. This convergent synthesis utilizes Jacobsen kinetic resolution, regioselective ring-opening of epoxide and Yamaguchi macrolactonization as key steps. 相似文献
90.
Oxidation of Ru(III)‐Bound Thiocyanate with Peroxomonosulfate: Kinetic and Mechanistic Studies
下载免费PDF全文
![点击此处可从《国际化学动力学杂志》网站下载免费的PDF全文](/ch/ext_images/free.gif)
The reaction of [RuIII(edta)(SCN)]2? (edta4? = ethylenediaminetetraacetate; SCN? = thiocyanate ion) with the peroxomonosulfate ion (HSO5?) has been studied by using stopped‐flow and rapid scan spectrophotometry as a function of [RuIII(edta)], [HSO5?], and temperature (15–30ºC) at constant pH 6.2 (phosphate buffer). Spectral analyses and kinetic data are suggestive of a pathway in which HSO5? effects the oxidation of the coordinated SCN? by its direct attack at the S‐atom (of SCN?) coordinated to the RuIII(edta). The high negative value of entropy of activation (ΔS≠ = ?90 ± 6 J mol?1 deg?1) is consistent with the values reported for the oxygen atom transfer process involving heterolytic cleavage of the O‐O bond in HSO5?. Formation of SO42?, SO32?, and OCN? was identified as oxidation products in ESI‐MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented. 相似文献