全文获取类型
收费全文 | 1195篇 |
免费 | 101篇 |
国内免费 | 579篇 |
专业分类
化学 | 1363篇 |
晶体学 | 26篇 |
力学 | 15篇 |
综合类 | 16篇 |
数学 | 170篇 |
物理学 | 285篇 |
出版年
2023年 | 1篇 |
2022年 | 34篇 |
2021年 | 35篇 |
2020年 | 26篇 |
2019年 | 7篇 |
2018年 | 16篇 |
2017年 | 56篇 |
2016年 | 50篇 |
2015年 | 76篇 |
2014年 | 123篇 |
2013年 | 120篇 |
2012年 | 201篇 |
2011年 | 189篇 |
2010年 | 101篇 |
2009年 | 96篇 |
2008年 | 115篇 |
2007年 | 136篇 |
2006年 | 59篇 |
2005年 | 82篇 |
2004年 | 86篇 |
2003年 | 54篇 |
2002年 | 33篇 |
2001年 | 18篇 |
2000年 | 30篇 |
1999年 | 19篇 |
1998年 | 17篇 |
1997年 | 18篇 |
1996年 | 23篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1985年 | 1篇 |
1983年 | 1篇 |
排序方式: 共有1875条查询结果,搜索用时 224 毫秒
1.
利用1,4-二-(4-羧基吡啶基)丁烷(L)合成了两个新的三维配位聚合物{(CdL2)·4H2O·2ClO4}n 1和{(ZnL2)·4H2O·2ClO4}n 2。单晶X-射线结构分析表明,1和2具有相同的计量式,但其晶体属于不同的空间群(1属于P4n2,2属于P4222)。两种配合物中,每个金属离子分别由配体与四个相邻的金属离子连接,从而形成具有六重穿插的金刚石网络结构,其网络中大的空腔被高氯酸根离子和(H2O)4分子簇所占据。 相似文献
2.
3.
4.
在H6TeO6/KOH水溶液中以臭氧为氧化剂,将二价铜化合物氧化成三价铜化合物,并获得一个新的三价铜化合物Ba4K[Cu(H2TeO6)2](OH)4.6H2O;描述了碱性溶液中“Cu(Ⅲ)/Cu(Ⅲ)”循环伏安图。对铜(Ⅲ)化合物,Na4H[H2TeO6)2].17H2O以及相应的铜(Ⅱ)配合物的电子光谱和Cu2pXPS进行了研究,给出了其配位场场强参数和Cu2PXPX的电子结合能。由于价态升高 相似文献
5.
呋喃甲醛缩二乙撑三胺希夫碱铜配合物的合成及结构(英) 总被引:1,自引:0,他引:1
A novel copper(Ⅱ) complex CuL(NO3)2(where L=N,N′-bis(furaldehyde)-diethylenetriamine) was synthesized and characterized by X-ray crystallography analysis. The crystal belongs to monoclinic, space group C2/c with cell parameters a=1.924 0(6) nm, b=0.792 8(3) nm, c=2.504 1(8) nm, β=111.163(5)°, and Z=8. The coordination geometry around Cu(Ⅱ) is a distorted trigonal-bipyramid,and one-dimensional chain is formed through intermolecular hydrogen bonds. CCDC: 255629. 相似文献
6.
A copper(Ⅱ) complex 1 of a novel macrocyclic polyamine ligand with hydroxylethyl pendant groups, 4,11-bis(hydroxylethyl)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (L) has been synthesized and characterized. Rate enhancement for hydrolysis of p-nitrophenyl picolinate (PNPP) catalyzed by 1 was studied kinetically under Brij35 micellar condition. For comparision, the catalytic activity of corresponding copper(Ⅱ) complex 2 of non-substituted macrocyclic polyamine ligand, 5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraaza-cyclotetradecane (L') toward the hydrolysis of PNPP was also investigated. The results indicate that the macrocyclic polyamine copper(Ⅱ) complex 1 effectively catalyzed the hydrolysis of PNPP, and the pendant ligand hydroxyl group or deprotonated pendant ligand hydroxyl group can act as catalytically active species in the reaction. A ternary Complex kinetic model involving metal ion, ligand and substrate has been proposed, and the results confirmed the reasonability of such kinetic model. 相似文献
7.
One novel complex [Co(p-MBA)2(2,2'-bipy)(H2O)]·(H2O) has been synthesized by the reaction of p-methylbenzoic acid with 2,2'-bipyridine in the solvent mixture of water and methanol. It crystallizes in triclinic, space group P-1 with a=0.70479(14), b=1.1211(2), c=1.6718(3) nm, α=103.806(3), β=90.795(3), γ=104.207(3)°, V=1.2399(4) nm3, Mr=512.41, Dc=1.373 g/cm3, Z=2, F(000)=532, μ=0.733 mm-1, R=0.0432 and wR=0.0957. The crystal structural analysis shows that the cobalt atom is coordinated with three oxygen atoms from two p-methylbenzoic acids and one water molecule and two nitrogen atoms from one 2,2'-bipyridine,forming a distorted square-pyramidal coordination geometry. The cyclic voltammetry behavior of the complex is also reported. 相似文献
8.
配位聚合物通常是通过某种有机配体与金属的配位几何选择以及无限网络的拓扑结构控制而形成的具有无限结构的化合物 [1] ,其结构新颖并具有不寻常的光电效应、非线性光学性能、磁性、超导及催化等诸多具有诱人应用前景的独特性能 .因此 ,近年来倍受化学家和材料学家的重视 [2~ 5] .以 Co为配位中心的配位聚合物若具有八面体构型 ,在一定条件下具有自旋转换能力 ,而且往往可与光电转换能力相关联 ,是一种潜在的新型信息存储材料 [6 ] .对于配位聚合物的形成 ,配体的选择最重要 . 4,4′-联吡啶及其衍生物是一种较好的刚性配体 ,相关的配位聚… 相似文献
9.
Irene Conti Marco Garavelli 《Journal of photochemistry and photobiology. A, Chemistry》2007,190(2-3):258-273
The effect of substitution on the intrinsic (i.e. in vacuo) photoisomerization ability of retinal chromophore models has been explored using CASPT2//CASSCF minimum energy path computations to map the S1 photoisomerization paths of two substituted minimal models of the retinal chromophore: the 2-cis-penta-2,4-dieniminium and the all-trans-epta-2,4,6-trieniminium cations, which have been modified using fluorine or methoxyl substituents as representative examples of electron-withdrawing and electron-releasing groups, respectively. A systematic analysis has been performed involving substitutions in all the possible positions along the chain. It is shown that the photochemical reactivity and photoisomerization efficiency of these systems may be tuned or indeed changed, although this effect strongly depends on the position of the substituent. In particular, we have shown that (i) most of the systems preserves qualitatively the reactivity of the parent (i.e. unsubstituted) compound; (ii) substitution at positions C4 or C6 leads to a different relaxed excited state structure of the chromophore and in general to a very flat photoisomerization path (or to a tiny S1 energy barrier in some cases); (iii) the nature of the TICT state (i.e. the S1 → S0 decay funnel) may be turned from a conical intersection into an excited state minimum; (iv) for the C4 methoxy-substituted system the isomerization path as well as the S1/S0 decay funnel involve an unusual torsional angle. Thus, substitution turns out to be a good tool not only to tune the optical properties (i.e. the absorption and emission features) of the chromophore (as we have already shown in a previous work: I. Conti, F. Bernardi, G. Orlandi, M. Garavelli, Mol. Phys. 104 (2006) 915–924), but it may also play a crucial role in tuning and controlling photoisomerization selectivity and efficiency, affecting excited state lifetime and reaction rate. A rationale for these effects is presented, which provides a basis for understanding reactivity properties and the intrinsic photochemical behavior of substituted retinal chromophores. 相似文献
10.
Pentacoordinate complex cations of the general formula [(C6F5)2SbL3]3+ stabilized as solid salts in combination with tetraphenylborate (BPh4), tetrafluorobroate (BF4) anions, where L=DMSO, Ph3AsO, PyO, DMF, α-, β- and γ-picoline have been isolated. The newly formed complexes were characterized by elemental analysis, molar conductance measurements, solid-state IR and and NMR. From these results, a five-fold coordination around antimony was required. 相似文献