全文获取类型
收费全文 | 678篇 |
免费 | 23篇 |
国内免费 | 1篇 |
专业分类
化学 | 466篇 |
晶体学 | 8篇 |
力学 | 15篇 |
数学 | 53篇 |
物理学 | 160篇 |
出版年
2023年 | 4篇 |
2022年 | 6篇 |
2021年 | 5篇 |
2020年 | 6篇 |
2019年 | 9篇 |
2018年 | 8篇 |
2017年 | 6篇 |
2016年 | 13篇 |
2015年 | 9篇 |
2014年 | 21篇 |
2013年 | 46篇 |
2012年 | 36篇 |
2011年 | 50篇 |
2010年 | 38篇 |
2009年 | 25篇 |
2008年 | 38篇 |
2007年 | 39篇 |
2006年 | 35篇 |
2005年 | 41篇 |
2004年 | 31篇 |
2003年 | 27篇 |
2002年 | 24篇 |
2001年 | 7篇 |
2000年 | 11篇 |
1999年 | 13篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 4篇 |
1995年 | 8篇 |
1994年 | 14篇 |
1993年 | 4篇 |
1992年 | 8篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1973年 | 7篇 |
1972年 | 3篇 |
1969年 | 3篇 |
1938年 | 3篇 |
1933年 | 2篇 |
1887年 | 2篇 |
排序方式: 共有702条查询结果,搜索用时 15 毫秒
1.
2.
Dr. Anton Lishchynskyi Dr. Fedor M. Miloserdov Dr. Eddy Martin Dr. Jordi Benet‐Buchholz Eduardo C. Escudero‐Adán Dr. Andrey I. Konovalov Dr. Vladimir V. Grushin 《Angewandte Chemie (International ed. in English)》2015,54(50):15289-15293
First evidence for the existence of free trifluoromethyl anion CF3? has been obtained. The 3D‐caged potassium cation in [K(crypt‐222)]+ is inaccessible to CF3?, thus rendering it uncoordinated (“naked”). Ionic [K(crypt‐222)]+ CF3? has been characterized by single‐crystal X‐ray diffraction, solution NMR spectroscopy, DFT calculations, and reactivity toward electrophiles. 相似文献
3.
Ugo Authesserre Sophie Hameury Aymeric Dajnak Nathalie Saffon-Merceron Antoine Baceiredo David Madec Eddy Maerten 《Molecules (Basel, Switzerland)》2021,26(7)
Due to their remarkable electronic features, recent years have witnessed the emergence of carbones L2C, which consist in two donating L ligands coordinating a central carbon atom bearing two lone pairs. In this context, the phosphine/sulfoxide-supported carbone 4 exhibits a strong nucleophilic character, and here, we describe its ability to coordinate dichlorogermylene. Two original stable coordination complexes were obtained and fully characterized in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis, respectively. At 60 °C, in the presence of 4, the Ge(II)-complex 5 undergoes a slow isomerization that transforms the bis-ylide ligand into an yldiide. 相似文献
4.
Jeroen Rintjema Dr. Wusheng Guo Dr. Eddy Martin Eduardo C. Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10754-10762
The chemoselective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six‐membered cyclic carbonates remains a challenging topic. Here, an effective method for their synthesis relying on the use of Al catalysis is described. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2‐ and 3‐position(s) of the oxetane ring. The presented methodology is the first general approach towards the formation of six‐membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six‐membered cyclic carbonates, also the unprecedented room‐temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five‐ and six‐membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers. 相似文献
5.
A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions 下载免费PDF全文
Dr. Christopher J. Wallis Dr. Gilles Alcaraz Dr. Alban S. Petit Dr. Amalia I. Poblador‐Bahamonde Dr. Eric Clot Dr. Christian Bijani Dr. Laure Vendier Dr. Sylviane Sabo‐Etienne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):13080-13090
We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a 15N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process. 相似文献
6.
7.
8.
Dr. Eddy W. T. Yemeli Dr. Graeme R. Blake Dr. Alexios P. Douvalis Prof. Thomas Bakas Gert O. R. Alberda van Ekenstein Dr. Petra J. van Koningsbruggen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(72):16766-16776
The iron(III) spin-crossover compounds [Fe(Hthsa)(thsa)] ⋅ H2O ( 1 ), [Fe(Hth5Clsa)(th5Clsa)2] ⋅ H2O ( 2 ), and [Fe(Hth5Brsa)(th5Brsa)2] ⋅ H2O ( 3 ) (H2thsa=salicylaldehyde thiosemicarbazone, H2th5Clsa=5-chlorosalicylaldehyde thiosemicarbazone, and H2th5Brsa=5-bromosalicylaldehyde thiosemicarbazone) have been synthesized and their spin-transition properties investigated by magnetic susceptibility, Mössbauer spectroscopy, and differential scanning calorimetry measurements. The three compounds exhibit an abrupt spin transition with a thermal hysteresis effect. The more polarizable the substituent on the salicylaldehyde moiety, the more complete is the transition at room temperature with an increased degree of cooperativity. The molecular structures of 1 and 2 in the high-spin state are revealed. The occurrence of the light-induced excited-spin-state trapping phenomenon appears to be dependent on the substituent incorporated into the 5-position of the salicylaldehyde subunit. Whereas the compounds with an electron-withdrawing group (-Br or -Cl) exhibit light-induced trapped excited high-spin states with great longevity of metastability, the halogen-free compound does not, even though strong intermolecular interactions (such as hydrogen-bonding networks and π stacking) operate in the system. For compound 2 , the surface level of photoconversion is less than 35 %. In contrast, compound 3 displays full photoexcitation. 相似文献
9.
10.