全文获取类型
收费全文 | 3881篇 |
免费 | 430篇 |
国内免费 | 738篇 |
专业分类
化学 | 4738篇 |
晶体学 | 98篇 |
力学 | 2篇 |
综合类 | 10篇 |
数学 | 25篇 |
物理学 | 176篇 |
出版年
2024年 | 3篇 |
2023年 | 27篇 |
2022年 | 89篇 |
2021年 | 156篇 |
2020年 | 225篇 |
2019年 | 176篇 |
2018年 | 149篇 |
2017年 | 147篇 |
2016年 | 225篇 |
2015年 | 187篇 |
2014年 | 225篇 |
2013年 | 324篇 |
2012年 | 461篇 |
2011年 | 251篇 |
2010年 | 218篇 |
2009年 | 237篇 |
2008年 | 248篇 |
2007年 | 249篇 |
2006年 | 216篇 |
2005年 | 184篇 |
2004年 | 232篇 |
2003年 | 158篇 |
2002年 | 91篇 |
2001年 | 76篇 |
2000年 | 65篇 |
1999年 | 84篇 |
1998年 | 51篇 |
1997年 | 47篇 |
1996年 | 39篇 |
1995年 | 30篇 |
1994年 | 27篇 |
1993年 | 24篇 |
1992年 | 30篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 6篇 |
1988年 | 19篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有5049条查询结果,搜索用时 15 毫秒
81.
82.
E. A. Fedorova N. V. Glushkova M. N. Bochkarev H. Schumann H. Hemling 《Russian Chemical Bulletin》1996,45(8):1996-1999
Reactions of naphthaleneeuropium and naphthaleneytterbium, C10H8Ln(DME) (Ln = Eu or Yb), with phenylacetylene are accompanied by the formation of the C-C bond and yield the complexes of composition Ph2C4H2Ln(DME)2. Hydrolysis of the Ph2C4H2Ln(DME)2 complexes affords a mixture of isomers of 1,4-diphenyl-1,3-butadiene. Reactions of C10H8[LnI(DME)2]2 with PhCCH yield mixed iodine-ethynyl complexes [ILn(-CCPh)(DME)2]2. According to the data of X-ray diffraction analysis, the ytterbium complex consists of two YbI(DME)2 units bonded through two bridging CCPh groups. The crystals of this complex belong to the space groupP21/c. The central cyclic Yb-C-Yb-C fragment is planar; the C(I)-Yb(I)-C(I) angle is 86.4(3)°. The Yb-C bond lengths are 2.584(8) and 2.603(9) Å.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 2101–2104, August, 1996. 相似文献
83.
In a reaction system consisting of FeCl2,tetrathiometallate and cycloalkylthiolate,two Fe4S4 cubane-like cluster compounds were obtained with the following crystallographic data:(PhCH2NMe32[Fe4S4 (SC5H9)4](Ⅰ),monoclinic space group P21/c,a=1.6327(4),6=1.1229(3),c=2.802 5( 10) nm,β=94.63(2)°,Z=4,and R=0.074; (Et4N)2[Fe4S4(SC6H11)4](Ⅱ),tetragonal space group I42m,a=1.16705(9),b=1.167 06(2),c=2.063 26(5) nm,Z=2,Dabs=1.28 g/cm3,and R=0.078 The participation of cy-cloalkylthiolate ligand does not obviously arouse the change of the Fe4S4 core structure.Meanwhile,the influence of the cation on the structural symmetry of the Fe4S4 cluster dianion is also discussed. 相似文献
84.
Liang Oyang Hao-Ling Sun Xin-Yi Wang Jun-Ran Li Dao-Bo Nie Wen-Fu Fu Song Gao Kai-Bei Yu 《Journal of Molecular Structure》2005,740(1-3):175-180
Ternary terbium complexes with p-aminobenzoic acid (HL), [TbL3(DMSO)(H2O)]2 (1), [TbL3(DMF)(H2O)]2 (2) and [TbL3(Bpy)(H2O)]2·2H2O (3) (DMSO=dimethyl sulfoxide, DMF=N, N- dimethylformamide, Bpy=2, 2′- bipyridyl) have been synthesized, and their crystal structures determined. The luminescence properties of these complexes, including both the emission quantum yield and the fluorescence lifetime, have been investigated. The effect of a second ligand on the crystal structure and luminescence property of the ternary terbium p-aminobenzoic acid complexes, and the relationship between luminescence properties and crystal structure, including coordination mode of the L− ligand and the characteristics of a second ligand, are discussed. 相似文献
85.
Rosenberg Edward Freeman William Carlos Zinnia Hardcastle Kenneth Yong Jin Yoo Milone Luciano Gobetto Roberto 《Journal of Cluster Science》1992,3(4):439-457
The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to 3-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in 3-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth. 相似文献
86.
A new Co(II) complex with tridentate Schiff base ligand with a N,N,O donor set has been synthesized and characterized by single X-ray technique and spectroscopic techniques. The thermochemical properties have been studied. X-ray structure analysis of the title compound Co(II)L2 [HL = 2-methyl-6-(2′-hydroxybenzylideneamino) pyridine] shows that the polyhedron around Co(II) is a distorted tetrahedron, and the self-assembly via intermolecular π-π interactions leads to a three-dimensional network. Crystal data for the title complex C26H22CoN4O2: Monoclinic, space group Ia, a = 11.741(7) Å, b = 8.149(5) Å, c = 22.764(16) Å, β = 98.530(12)°, V = 2154(2) Å3, Z = 4. 相似文献
87.
Mixed-ligand NiIII complexes with -nitroso--naphthol, -nitroso--naphthol,o-ethylxanthate, andN,N-diethyldithiocarbamate as ligands have been studied by ESR in liquid and frozen solutions. The degrees of symmetry distortion for the first coordination sphere of these complexes have been determined. It is shown that the transition from planar square NiIIL2 complexes to more stable octahedral NiIIIL2L and NiIIILL2 complexes occursvia the radical addition mechanism. A method for trapping short-lived radicals is suggested on the basis of the complex formation scheme.Translted fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1513–1515, August, 1995.The work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-5050) 相似文献
88.
89.
Synthesis and Crystal Structure of Bis(1,2-dimetyl-5-nitro-imidazole)dichlorocobalt(II) Bis(1,2-dimethyl-5-nitro-imidazol)dichlorocobalt(II) was obtained by reaction of CoCl2 · 6 H2O with 1,2-dimethyl-5-nitro-imidazole in methanol. The compound forms blue crystals which were characterized by IR and UV-vis spectroscopy and by an X-ray crystal structure determination. Co(C5H7N3O2)2Cl2: tetragonal, space group I4 2d, Z = 8, a = 1142.1(1) pm, c = 2577.3(2) pm. R = 0.036 for 670 independent reflexions. The Co atom is tetrahedrally surrounded by two chlorine and two N atoms at distances of 222.8(2) and 203.5(4) pm. 相似文献
90.
The reaction of Os3(CO)10(NCMe)[Si(OMe)3](-H),1, with PMe2Ph yielded the new complex Os3(CO)10(PMe2Ph)[Si(OMe)3](-H),2 by substitution of the MeCn ligand with the phosphine ligand. When heated to 125°C compound2 was decarbonylated and transformed into the new unsaturated cluster complex Os3(CO)8[-PMe2(C6H4)][Si(OMe)3](-H)2,3 in 54% yield. Compound3 was characterized by a single crystal X-ray diffraction analysis, osmium bonds. The phenyl ring of the phosphine ligand has undergoneortho-metallation by a neighboring metal atom. A terminally coordinated Si(OMe)3 ligand is coordinated to the third osmium atom. The cluster is unsaturated by the amount of 2 electrons, and there is an open coordination site on the siloxyl substituted osmium atom that is partially filled by a weak interaction with one of the -bonds of theortho-metalled phenyl ring. Complex3 reacts with CO at 1 atm to reform compound2 in 85% yield in 5 h at 40°C. Crystal Data: for3: space group = P21/n,a = 9.911(2) Å,b = 18.451(6) Å,c = 14.872(2) Å, = 95.64(2)°,Z = 4, 1994 reflections,R = 0.028. 相似文献