全文获取类型
收费全文 | 603篇 |
免费 | 60篇 |
国内免费 | 270篇 |
专业分类
化学 | 864篇 |
晶体学 | 9篇 |
综合类 | 6篇 |
物理学 | 54篇 |
出版年
2024年 | 5篇 |
2023年 | 13篇 |
2022年 | 17篇 |
2021年 | 27篇 |
2020年 | 38篇 |
2019年 | 18篇 |
2018年 | 18篇 |
2017年 | 23篇 |
2016年 | 31篇 |
2015年 | 23篇 |
2014年 | 33篇 |
2013年 | 79篇 |
2012年 | 44篇 |
2011年 | 28篇 |
2010年 | 18篇 |
2009年 | 32篇 |
2008年 | 30篇 |
2007年 | 42篇 |
2006年 | 37篇 |
2005年 | 22篇 |
2004年 | 43篇 |
2003年 | 44篇 |
2002年 | 39篇 |
2001年 | 20篇 |
2000年 | 21篇 |
1999年 | 27篇 |
1998年 | 18篇 |
1997年 | 11篇 |
1996年 | 16篇 |
1995年 | 17篇 |
1994年 | 10篇 |
1993年 | 10篇 |
1992年 | 18篇 |
1991年 | 13篇 |
1990年 | 12篇 |
1989年 | 9篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1975年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有933条查询结果,搜索用时 296 毫秒
1.
采用Cundari和Stevens等推导的有效芯势对镧系金属一氢化物进行了理论计算,以探讨镧系金属元素与氢的相互作用。结果表明所有镧系金属一氢化物基态时理论上是稳定的,最稳定的是SmH,最不稳定的是DyH;键长计算结果显示,基态时镧系金属一招兵买马花物有独立王国 收缩现象发生;红外振动频率理论计算值与实验结果一致;成键轨道中,金属原子轨道的贡献主要是s轨道和d轨道:从CeH至ErH(GdH)例外)随着外层电子的增加s轨道成分逐渐增大d轨道成分逐渐减小;从TmH和LuH(包括GdH),成键轨道中金属原子轨道的贡献主要是d轨道,约为90%;约大多数镧系金属一氧化物的成键轨道中金属原子轨道f成分小于1%。 相似文献
2.
Calcium lanthanide oxyborate doped with rare-earth ions LnCa4O(BO3)3:RE3+ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band Ect were calculated and compared with their excitation spectra.Eu3+ and Tb3+ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce3+ ions do not show efficient luminescence and quench the luminescence of Tb3+ ions when Tb3+ and Ce3+ ions are co-doped into LnCOB. GdCOB doped with Dy3+ shows yellowish white light under irradiation of 254 nm light for the reason that Gd3+ ions transfer the energy from itself to Dy3+. Because of the existence of Gd3+, the samples of GdCOB:RE3+ show higher excitation efficiency than LaCOB:RE3+ and YCOB:RE3+, around 188 nm, which indicates that the Gd3+ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb3+, Dy3+ and Eu3+. 相似文献
3.
In this paper, according to the molecular fragment principle, a series of eight ternary luminescent lanthanide complex systems were assembled, and whose compositions were determined with elemental analysis and infrared spectrum: Ln(MA)3(L)·H2O, where Ln = Sm, Eu, Tb, Dy; HMA = α‐methylacrylic acid; L = 1,10‐phenanthroline (phen), 2,2′‐bipyridine (bipy). The photophysical properties of these functional molecular systems were studied with ultraviolet‐visible absorption spectrum, and fluorescence excitation and emission spectrum. It was found that the heterocylic compounds (phen and bipy) act as the main energy donor and luminescence sensitizer for their suitable energy match and effective energy transfer to the emission energy level of Ln3+ ions. MMA ligand was only used as the terminal structural ligand to influence the luminescence. Especially terbium complex systems show the strongest luminescence for the optimum energy match and transfer between phen (bipy) and Tb3+ ion. 相似文献
4.
Lanthanide Complexes for Oligomerization of Phenyl Isocyanate 总被引:1,自引:0,他引:1
IntroductionThestudyonthereactivitiesoflanthanidecomplexesto wardisocyanateshasattractedmuchattention .Ithasbeenre portedthatlanthanidealkoxides,1anddivalentdiaza pentadi enyllanthanidecomplexes2 canbeusedasthesinglecompo nentinitiatorsforisocyanatespolymerization .Recentlyourre searchgrouphasalsofoundthatlanthanoceneamide ,3diva lentaryloxideofsamarium4 ,5anddivalentsamarocene6 areallactivefortheoligomerizationofphenylisocyanate,andtheactivespeciesforthesethreesystemswereallsuccessfullyisolat… 相似文献
5.
The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed. 相似文献
6.
7.
Jun Fan Wei‐Guang Zhang Min‐Yu Tan Yu Tang Wei‐Sheng Liu Ning Tang Kai‐Bei Yu 《中国化学》2004,22(6):508-511
The La(III) complex with a new amide‐type tripodal ligand,2,2′.2″‐nitrilotris{[(2′‐benzylaminofomyl)‐phenoxylethyl)amine (L), was synthesized and characterized by X‐ray crystallographic analysis. Crystal data: C48H55.50LaN7O18.75, Mr=1169.40, monoclinic. space group, P21/n, a= 1.0644(3) nm. b=2.3889(5) nm, c= 2.1917(5) nm, β=90.65°, V=5.573(2) nm3, Z=1, Dc=1.394 g°cm?3, R1=0.0487, wR [1>2s?(I)]=0.1266. The results reveal that each La(III) ion binds to 9 oxygen atoms, three of which belong to carbonyl groups from three tripodal ligands and six to three bidentate nitrate groups and a two‐dimensional sheet of 4.82 networks is assembled by metal‐ligand coordination interaction. L, a heptadentate compound, merely acts as a tridentate bridging spacer due to its steric hindrance and links the La(III) ions as three‐connected nodes. 相似文献
8.
二茂铁液晶因其独特的稳定性和易于衍生化受到研究人员的青睐[1- 8] 。我们曾经报道过一类单取代二茂铁液晶的合成与介晶性[9] 。这里我们报道另外一类二茂铁单取代液晶 ,并对分子的长度、溴原子取代对介晶性的影响进行探讨。合成路线如下 :1 实验部分BruckerACE -2 0 0spectrometer,CDCl3作溶剂。NicoletMagna-IR 5 0 0Spectrometer,SeriesⅡ ,KBr压片。WRS -IA ,CarloErba 1 1 0b。Perkin -Elmer 7Series热分析仪 ,分温速度 1 0℃ /mi… 相似文献
9.
P. Miranda Jr. J. Zukerman-Schpector J. R. Matos M. F. Máduar E. M. Aricó M. Linardi L. B. Zinner G. Vicentini 《Journal of Thermal Analysis and Calorimetry》2004,75(2):577-582
The complexes [Ln(pic)3(DTSO)3] (Ln=La, Lu and Y; pic=picrate; DTSO=1,3-dithiane-1-oxide) were synthesized and characterized. Indirect structural determination by far infrared
spectroscopy is presented. Results from thermal decomposition of these complexes by TG/DTG and DSC techniques are reported.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
10.
0IntroductionThefirstmolecule鄄basedmagnetswerereportedin1986[1].Duringthelasttwodecades,moreandmoreattentionhasbeenpaidtothesynthesisofmolecule鄄basedmagnets,especiallytoPrussianBlueanalogu鄄es[2].TheoldPrussianBlueanalogueshavebeenbroughtuptodateduetoth… 相似文献