全文获取类型
收费全文 | 868篇 |
免费 | 198篇 |
国内免费 | 42篇 |
专业分类
化学 | 775篇 |
晶体学 | 7篇 |
力学 | 2篇 |
综合类 | 4篇 |
数学 | 67篇 |
物理学 | 253篇 |
出版年
2023年 | 10篇 |
2022年 | 7篇 |
2021年 | 27篇 |
2020年 | 32篇 |
2019年 | 32篇 |
2018年 | 22篇 |
2017年 | 31篇 |
2016年 | 63篇 |
2015年 | 56篇 |
2014年 | 60篇 |
2013年 | 65篇 |
2012年 | 62篇 |
2011年 | 55篇 |
2010年 | 42篇 |
2009年 | 56篇 |
2008年 | 52篇 |
2007年 | 58篇 |
2006年 | 43篇 |
2005年 | 42篇 |
2004年 | 32篇 |
2003年 | 33篇 |
2002年 | 30篇 |
2001年 | 20篇 |
2000年 | 21篇 |
1999年 | 19篇 |
1998年 | 20篇 |
1997年 | 15篇 |
1996年 | 24篇 |
1995年 | 10篇 |
1994年 | 5篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 7篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 7篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1959年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有1108条查询结果,搜索用时 31 毫秒
121.
《Angewandte Chemie (International ed. in English)》2017,56(43):13470-13474
The regioselective transformation of heterobuckybowl trichalcogenasumanenes 1 a , b at peripheral butoxy groups afforded trichalcogenasumanene ortho ‐quinones 2 a , b . Compounds 2 a , b are distinct from 1 a , b in terms of their molecular geometry and electronic state; that is, they have a shallower bowl depth and show absorbance in the NIR region. The reaction of 2 a , b with diamines resulted in a variety of heteropolycycles, including molecular spoon 3 a – 6 a , planar π‐systems 3 b – 6 b , and highly twisted [7‐6‐6]‐fused systems 7 a , b . These new heteropolycycles had different optical/electrical properties: 4 a,b showed hole mobility of approximately 0.002 cm2 V−1 s−1, 6 a displayed red emission in both solution and the solid state, and 7 a , b formed tight stacks of the curved π‐surface. 相似文献
122.
Kengo Asai Prof. Dr. Aiko Fukazawa Prof. Dr. Shigehiro Yamaguchi 《Angewandte Chemie (International ed. in English)》2017,56(24):6848-6852
A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H+ ) and an anion ( 1− ). While 1H+ showed an intense fluorescence in the red region of the visible spectrum, 1− exhibited a strong absorption in the NIR region. The tropylium ion character in 1H+ induces high pKa1 and pKa2 values for 1 . Moreover, a stable radical ( 1. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1. revealed a two-step reversible redox process that produced 1− and the cation 1+ , which is different from 1H+ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton. 相似文献
123.
近年来,新型有机非富勒烯受体的开发极大地促进了有机聚合物太阳能电池效率的不断突破。其中具有空间非平面结构的新型非富勒烯受体材料是该领域的一个研究热点。本文选取1,8-萘酰亚胺(NMI)作为受电子单元,合成制备了基于螺[4,4]双环戊[2,1-b∶3,4-b′]二噻吩核心单元的空间非平面化合物SCPDT-(NMI)4及对应的基于环戊[2,1-b∶3,4-b′]二噻吩以及环戊[2,1-b∶3,4-b′]二噻吩-4-酮的线性模型化合物CPDT-(NMI)2和CPDT-O-(NMI)2。在此基础上,详细研究了3个化合物的光谱吸收、荧光光谱以及循环伏安电化学性质。结果表明,具有螺形结构的SCPDT-(NMI)4因其非平面结构以及较高的分子内空间位阻,导致其吸收光谱与线性化合物CPDT-(NMI)2相比出现了11nm的蓝移。固体薄膜吸收光谱结果表明,这一系列化合物具有弱的分子间相互作用。电化学循环伏安测试结果表明,所合成的3个化合物均有可逆的氧化还原过程。据此测得化合物的LUMO能级大致为-3.5~-3.8eV之间,可作为电子受体用于有机薄膜光伏电池。利用所合成的萘酰亚胺修饰的化合物作为电子受体,PBDB-T作为电子给体制备了有机太阳能电池器件。器件实验结果表明,基于空间非平面SCPDT-(NMI)4的器件光电转换效率达到了1.16%,远高于以线性分子CPDT-(NMI)_2作为受体的器件效率(0.11%)。荧光光谱猝灭实验结果表明,所合成的萘酰亚胺化合物与聚合物之间不完全的电子转移是影响器件性能的最主要因素。 相似文献
124.
《化学:亚洲杂志》2017,12(20):2749-2762
A novel class of β‐functionalized push–pull zinc opp ‐dibenzoporphyrins were designed, synthesized, and utilized as sensitizers for dye‐sensitized solar cells. Spectral, electrochemical, and computational studies were systematically performed to evaluate their spectral coverage, redox behavior, and electronic structures. These porphyrins displayed much broader spectral coverage and more facile oxidation upon extension of the π conjugation. Free‐energy calculations and femtosecond transient absorption studies (charge injection rate in the range of 1011 s−1) suggested efficient charge injection from the excited singlet state of the porphyrin to the conduction band of TiO2. The power conversion efficiency (η ) of YH3 bearing acrylic acid linkers (η =5.9 %) was close to that of the best ruthenium dye N719 (η =7.4 %) under similar conditions. The superior photovoltaic performance of YH3 was attributed to its higher light‐harvesting ability and more favorable electron injection and collection, as supported by electrochemical impedance spectral studies. This work demonstrates the exceptional potential of benzoporphyrins as sensitizers for dye‐sensitized solar cells. 相似文献
125.
《化学:亚洲杂志》2017,12(5):561-567
We describe herein the first synthesis of silyl‐ and disilanyl‐BODIPYs through transition‐metal‐catalyzed dehalosilylation of iodo‐BODIPYs using a Pd(P(t Bu)3)2/Et3N/toluene system. Various mono‐ and bis‐silyl‐BODIPYs, mono‐ and bis‐disilanyl‐BODIPYs and bis‐BODIPYs linked by silylene and SiOSi groups were synthesized by using this straightforward method. Silyl‐ and disilanyl‐substitution significantly modifies the spectroscopic properties of the BODIPY, in which the fluorescence quantum yields of the silyl‐BODIPYs are remarkably increased, whereas the emission spectra of disilanyl‐BODIPYs are red‐shifted due to effective σ(SiSi)–π(BODIPY) conjugation. 相似文献
126.
Januszewski E Lorbach A Grewal R Bolte M Bats JW Lerner HW Wagner M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(45):12696-12705
The targeted hydrolysis of the 9,10-dihydro-9,10-diboraanthracene adduct (Me(2)S)HB(C(6)H(4))(2)BH(SMe(2)) (1) with 0.5 equiv of H(2)O leads to formation of the borinic acid anhydride [(Me(2)S)HB(C(6)H(4))(2)B](2)O (2) and thereby provides access to the field of unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes. Compound 2 reacts with tBuC≡CH to give the corresponding vinyl derivative in an essentially quantitative conversion. Subsequent cleavage of the B-O-B bridge by LiAlH(4) with formation of hydridoborate functionalities is possible but is accompanied by partial B-C(vinyl) bond degradation. This situation changes when the related mesityl derivative [MesB(C(6)H(4))(2)B](2)O (7) is employed, which can be synthesized from BrB(C(6)H(4))(2)BBr (6) by treatment with 1 equiv of MesMgBr and subsequent hydrolysis. The reaction of 7 with LiAlH(4) in tetrahydrofuran (THF) furnishes Li[MesB(C(6)H(4))(2)BH(2)] (8); hydride elimination with Me(3)SiCl leads to formation of the THF adduct MesB(C(6)H(4))(2)BH(THF) (9·THF). Alternatively, 7 can be transformed into the bromoborane MesB(C(6)H(4))(2)BBr (10) by treatment with BBr(3). A Br/H-exchange reaction between 10 and Et(3)SiH yields the donor-free borane MesB(C(6)H(4))(2)BH (9), which forms B-H-B bridged dimers (9)(2) in the solid state. The vinyl borane MesB(C(6)H(4))(2)BC(H)=C(H)Mes (14) is accessible from MesC≡CH and either 9·THF or 9. Compared with the related compound Mes(2)BC(H)=C(H)Mes, the electronic absorption and emission spectra of 14 reveal bathochromic shifts of Δλ(abs)=17 nm and Δλ(em)=74 nm, which can be attributed to the rigid, fully delocalized π framework of the [MesB(C(6)H(4))(2)B] chromophore. 相似文献
127.
128.
Ma CQ Pisula W Weber C Feng XL Müllen K Bäuerle P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(5):1507-1518
Three-dimensional (3D) π-conjugated dendritic oligothiophenes up to a third generation have been functionalized with tris(decyloxy)phenylethynyl tails at the periphery. The first-generation compounds (3 T-p-Ph-C10 and 6 T-p-Ph-C10) were synthesized by palladium-catalyzed Sonogashira coupling reactions, whereas the higher generation products were synthesized by palladium-catalyzed Suzuki coupling reactions in a divergent approach. The optical and electrochemical properties were investigated by UV/Vis absorption, fluorescence spectroscopy, and cyclic voltammetry. The results revealed that the terminal tris(alkyloxy)phenylethynyl groups are conjugated to the branched oligothiophene core, yielding redshifted absorption and fluorescence spectra and reduced optical band gaps relative to the dendritic oligothiophene core. A structural study revealed a close relationship between the type of supramolecular organization and the size of the oligothiophene core. The first-generation compounds 3 T-p-Ph-C10 and 6 T-p-Ph-C10 displayed columnar phases in the bulk state, which was confirmed by two-dimensional wide-angle X-ray scattering (2D WAXS) measurements. The self-assembly into columnar stacks has mainly been attributed to phase separation between the rigid thiophene cores and the flexible side-chains assisted by minor π-stacking interactions between the conjugated dendritic oligothiophene units. The high-generation compounds, however, showed less ordered structures in the solid state. 相似文献
129.
130.