全文获取类型
收费全文 | 12694篇 |
免费 | 778篇 |
国内免费 | 766篇 |
专业分类
化学 | 13320篇 |
晶体学 | 139篇 |
力学 | 7篇 |
综合类 | 26篇 |
数学 | 152篇 |
物理学 | 594篇 |
出版年
2023年 | 98篇 |
2022年 | 257篇 |
2021年 | 297篇 |
2020年 | 422篇 |
2019年 | 337篇 |
2018年 | 283篇 |
2017年 | 278篇 |
2016年 | 366篇 |
2015年 | 263篇 |
2014年 | 334篇 |
2013年 | 752篇 |
2012年 | 1323篇 |
2011年 | 509篇 |
2010年 | 448篇 |
2009年 | 623篇 |
2008年 | 706篇 |
2007年 | 854篇 |
2006年 | 656篇 |
2005年 | 610篇 |
2004年 | 600篇 |
2003年 | 498篇 |
2002年 | 406篇 |
2001年 | 358篇 |
2000年 | 353篇 |
1999年 | 335篇 |
1998年 | 289篇 |
1997年 | 285篇 |
1996年 | 307篇 |
1995年 | 311篇 |
1994年 | 214篇 |
1993年 | 184篇 |
1992年 | 152篇 |
1991年 | 105篇 |
1990年 | 62篇 |
1989年 | 51篇 |
1988年 | 51篇 |
1987年 | 42篇 |
1986年 | 38篇 |
1985年 | 29篇 |
1984年 | 31篇 |
1983年 | 12篇 |
1982年 | 26篇 |
1981年 | 14篇 |
1980年 | 18篇 |
1979年 | 12篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
991.
I. G. Filippova Yu. A. Simonov M. Gdanets V. Stavila 《Journal of Structural Chemistry》2005,46(6):1095-1098
The structure of tris(1,10-phenanthroline)iron(II) dinitrate dihydrate [Fe(phen)3](NO3)2·2H2O was established by X-ray diffraction analysis. The role of hydrogen bonds in crystal packing is discussed. 相似文献
992.
Joanna Taraszewska Magorzata Ko
bia 《Journal of inclusion phenomena and macrocyclic chemistry》2005,53(3):155-161
Complexation of ketoconazole (KET), a broad-spectrum antifungal drug, with β- and γ-cyclodextrins (CDs), heptakis (2,6-di-O-methyl)-β-CD (2,6-DM-β-CD), heptakis (2,3,6-tri-O-methyl)-β-CD (TM-β-CD), 2-hydroxypropyl-β-CD (2HP-β-CD) and carboxymethyl-β-CD (CM-β-CD) was studied. The stability constants were determined by the solubility method at pH = 6 and for 2,6-DM-β-CD and CM-β-CD at pH = 5. At pH = 6, the stability constants increased in the order: TM-β-D < γ-CD < 2HP-β-CD < β-CD < CM-β-CD < 2,6-DM-β-CD. At pH = 5, due to the increased ionization of KET, the stability constant with CM-β-CD increased and with 2,6-DM-β-CD decreased. For complexes of KET with 2HP-β-CD and 2,6-DM-β-CD, the thermodynamic parameters of complexation were determined from the temperature dependence of the corresponding stability constants. For β–γ and TM-β-CD complexes, calculations using HyperChem 6 software by the Amber force field were carried out to gain some insight into the host–guest geometry. 相似文献
993.
Hieronim Maciejewski Agnieszka Sydor Maciej Kubicki 《Journal of organometallic chemistry》2004,689(19):3075-3081
Reactions of the nickel(0) complexes [Ni(cod)2] (in the presence of PP or [Ni(PPh3)2C2H4] with vinyl-siloxanes, -silanes or -silazanes yield, by displacement of alkene ligand, the new nickel π-complexes [Ni(PPh3)2(η-CH2CHSi(OSiMe3)3)] (2), [{Ni(PPh3)}2{μ-(η-{(CH2CH)2SiMe}2O})] (4), [Ni(PPh3){η4-CH2CHSi(Me)(μ-O)}3] (5), [{Ni(η-CH2CHSiMe2)2O}(η-CH2CHSiMe3)] (7) and the known complexes [Ni(PPh3)2(η-CH2CHSiMe3)] (1), [{Ni(PPh3)}2{μ-(η-(CH2CH)4Si})] (3), [{Ni(PPh3)(η-CH2CHSiMe2)2NH}] (6) obtained by a simple one pot synthesis, more efficiently than in hitherto published reports. The X-ray crystal structure of (1) shows a trigonal planar environment around the nickel atom. 相似文献
994.
合成了两个异亚硝基乙酰丙酮 N 芳基亚胺的Pd(Ⅱ )配合物 ,PdCl(C6H5—IAI) (C6H5NH2 ) ( 1 )和PdCl( p CH3 C6H4 —IAI) ( p CH3 C6H4 NH2 ) ( 2 ) ,并测定了配合物 1的晶体结构 .配合物 1晶体属正交晶系 ,空间群为Pca2 1,晶胞参数a =1 .8587( 4 )nm ,b=0 .93 80 ( 2 )nm ,c=2 .1 2 3 7( 4 )nm ,Z =8,F( 0 0 0 ) =1760 ,μ =1 .1 60mm-1,R1=0 .0 2 71 .二齿Schiff碱配体的异亚硝基 (肟基 )的N原子和亚胺的N原子 ,苯胺基N原子和Cl-离子与Pd(Ⅱ )配位 ,形成PdN3 Cl平面正方形配位构型 .红外和喇曼光谱表明 ,形成配合物后νCO和νCN移向低频 ,而νN—O则移向高频 .电子光谱说明存在π π 和d π 跃迁 相似文献
995.
996.
合成了4种α-二亚胺镍催化剂Ar—NC(R1)C(R2)N—ArNiBr2[Ar=2,6-dimethylphenyl,R1=CnH2n+1,R2=CmH2m+1;其中Cat1:m=1,n=1;Cat2:m=2,n=1;Cat3:m=3,n=1;Cat4:m=2,n=2],考察了聚合温度、催化剂浓度和催化剂配体骨架碳原子上烷基取代基对乙烯聚合反应活性、聚合物链结构和结晶性能的影响.实验发现,当配体骨架上烷基取代基R1和R2不同时,催化剂具有较高的活性,且聚合物分子量也较高;其中,Cat2和Cat3在20℃,乙烯常压和5.8mmol/L催化剂用量下,乙烯聚合活性达1.86×103kgPE/(molNi.h)和1.92×103kgPE/(molNi.h),聚合物分子量(Mw)达6.82×105和1.019×105.聚乙烯链结构分析表明,甲基支链在聚乙烯支链中占主导地位,支化度主要受反应温度的影响;同时还发现,配体骨架碳原子上烷基取代基不同的二亚胺镍催化合成聚乙烯的长支链比例相对较高,特别是在较高反应温度40℃下,己基及以上长支链比例明显增加. 相似文献
997.
We report new chiral bisimidazolium salts synthesized from naturally occurring l-amino acids. They served as precursors for bidentate N-heterocyclic carbene metal complexes. The chiral imidazoles could be synthesized in good yields via a one-pot ring closing reaction, followed by esterification. The methylene bridged bisimidazolium iodide salts are accessible in moderate yields. Corresponding palladium(II)- and platinum(II)-NHC complexes could be synthesized and fully characterized, but do not show optical activity. We also report a solid state structure of one of the synthesized palladium(II) biscarbene compounds derived from alanine. 相似文献
998.
The synthetic investigation of the CuII/maleamate(−1) ion (HL−)/N,N′,N′′-chelate general reaction system has allowed access to compounds [Cu2(HL)2(bppy)2](ClO4)2·H2O (1·H2O), [Cu(HL)(bppy)(ClO4)] (2) and [Cu(HL)(terpy)(H2O)](ClO4) (4) (bppy = 2,6-bis(pyrazol-1-yl)pyridine, terpy = 2,2′;6′,2′′-terpyridine). In the absence of externally added hydroxides, compound [Cu2(L′)2(bppy)2](ClO4)2 (3) was obtained from MeOH solutions; L′− is the monomethyl maleate(−1) ligand which is formed in situ via the CuII-assisted HL− → L′− transformation. In the case of tptz-containing (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) reaction systems, the CuII-assisted hydrolysis of tptz to pyridine-2-carboxamide (L1) afforded complex [Cu(L1)2(NO3)2] (5). The crystal structures of 1–5 are stabilized by intermolecular hydrogen bonding and π–π stacking interactions. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. 相似文献
999.
Evangelia S. Koumousi Catherine P. Raptopoulou Spyros P. Perlepes Albert Escuer Theocharis C. Stamatatos 《Polyhedron》2010
The use of di-2-pyridyl ketone oxime, (py)pkoH, and phenyl 2-pyridyl ketone oxime, ppkoH, in copper(II) hexafluoroacetylacetonate chemistry is reported. The reaction of CuCl2·2H2O with one and two equivalents of ppkoH and Na(hfac), respectively, in CH2Cl2 affords the dinuclear complex [Cu2(hfac)2(ppko)2] (1) in excellent yield. The replacement of ppkoH by (py)pkoH gives the isostructural compound [Cu2(hfac)2{(py)pko}2] (2) in good yield. The CuII atoms in both 1 and 2 are doubly bridged by the oximate groups of two η1:η1:η1:μ2 ppko− and (py)pko− ligands, respectively. The bridging Cu–(R–NO)–Cu′ units are not planar, with the torsion angles being 23.2° (1) and 20.3° (2). A bidentate chelating hfac− ligand completes five-coordination at each square pyramidal metal ion. The hfac−-free reaction system CuCl2·2H2O/(py)pkoH/NEt3 (1:2:1) gives instead the mononuclear complex [CuCl{(py)pko}{(py)pkoH}] (3) in very good yield. The CuII atom is coordinated by two N,N′-bidentate (py)pko−/(py)pkoH chelates and a monodentate chloride anion resulting in a distorted square pyramidal geometry around the metal center. Variable-temperature, solid-state dc magnetic studies were carried out on the representative dinuclear complex 1 in the 2.0–300 K range. The data indicate a very strong antiferromagnetic exchange interaction and a resulting S = 0 ground state, which is well isolated from the S = 1 excited state. The J value of −720 cm−1 was derived from the fitting of the experimental data using the Hamiltonian H = −J(S1 · S2). 相似文献
1000.
Duraiswamy SukanyaDuraisamy Senthil Raja Nattamai S.P. BhuvaneshKaruppannan Natarajan 《Polyhedron》2011,30(6):1108-1113
New hexa-coordinated Ru(III) complexes of the type [Ru(H2Pzdc)(EPh3)3X2] have been synthesized by reacting 3,5-pyrazole dicarboxylic acid (H3Pzdc) with the appropriate starting complexes [RuX3(EPh3)3] (where X = Cl or Br; E = P or As). The ligand behaves as a bidentate monobasic chelate. All the complexes have been characterized by analytical and spectroscopic (IR, electronic and EPR) data. Single-crystal X-ray analysis of the complex [Ru(H2Pzdc)(PPh3)2Cl2]·C6H6·C2H5OH revealed that the coordination environment around the ruthenium center consists of an NOP2Cl2 octahedron. The planar ligand occupies the equatorial position along with two chlorine atoms, while the triphenylphosphine groups occupy the axial positions. The electrochemical behavior of the new complexes was studied using cyclic voltammetry. The new mononuclear ruthenium complexes are capable of acting as catalysts for the oxidation of alcohols. 相似文献