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111.
(RCp)_2MCl_2,(RCp)TiCl_3分别与N-(4-苯基-2-噻唑基)二硫代氨基甲酸钾和3-苯基-5-(2-呋哺基)-吡唑啉-1-二硫代甲酸钠进行反应,合成了三十二个未见报道的(RCp)M(S_2CNHR′)_nCl_(3-n),(RCp)_2M-(S_2CNHR′)_nCl_(2-n),[R=H,Me;M=Ti,Zr;R′=4-苯基噻唑基(PTDTC),n=1,2,3]以及(RCp)M(S_2CR~2)_nCl_(3-n),(RCp)_2M(S_2CR~2)_nCl_(2-n)[R=H,Me;M=Ti,Zr,R~2=3-苯基-15-(呋喃-2)吡唑啉基(PFPDTC),n=1,2,3]型配合物。所有配合物经元素分析、UV、IR和'H NMR谱证实,二硫代氨基甲酸是以双齿配体键合的。 相似文献
112.
Mizukami Fujio Maeda Kazuyuki Toba Makoto Sano Tsuneji Niwa Shu-ich Miyazaki Mitsuharu Kojima Kunihiko 《Journal of Sol-Gel Science and Technology》1997,8(1-3):101-106
The preparation of mullite by the sol-gel method using organic polydentate ligands and the effect of the raw materials and
organic polydentate ligands on the formation of mullite were investigated. Two series of samples were prepared using tetraethoxyorthosilicate
(TEOS) and aluminum nitrate nonahydrate, or dibutoxyethylacetoacetatoaluminum (Al(OBu)2(AcAcEt)) as the silica and alumina sources, respectively, and using ethylene glycol (EG), 1,3-propanediol (PD), 1,3-butanediol
(BD), 2-methyl-2, 4-pentanediol (MPD), diethlene glycol monoethyl ether (DEME) and ethoxyethanol as the ligands. When the
alumina source was aluminum nitrate nonahydrate, mullite was apt to appear in the order of EG>PD>MPD. When Al(OBu)2(AcAcEt) was the alumina source, the tendency toward the appearance of mullite crystalline phase was EG>BD>DEME>MPD. Between
the two alumina sources, aluminum nitrate nonahydrate gave mullite much easier than Al(OBu)2(AcAcEt). These relationships were discussed from the viewpoints of the coordination ability of the ligands and the miscibility
between the silica and alumina. 相似文献
113.
Pasynskii A. A. Grigoriev V. N. Torubaev Yu. V. Blokhin A. I. Shapovalov S. S. Dobrokhotova Zh. V. Novotortsev V. M. 《Russian Chemical Bulletin》2003,52(12):2689-2700
Transmetallation of the dichalcogenide complexes [CpMn(CO)2]2(-X2) (X = S or Se) with M(CO)5(thf) (M = Cr or W) afforded new heterometallic complexes CpMn(CO)2(-Se2)Cr(CO)5, CpMn(CO)2(-Se2)[Cr(CO)5]2, CpMn(CO)2(-X2)[W(CO)5]2 (X = S or Se), and CpMn(CO)2(-Se2)[Cr(CO)5][W(CO)5]. According to the X-ray diffraction data, their molecular structures contain the cyclic MnX2 fragments coordinated by one or two M(CO)5 groups via the X atoms. Study of thermal decomposition of the manganese complexes with different Mn : M : X ratios (M = Cr, W; X = S, Se, Te) by differential scanning calorimetry (DSC) and thermogravimetry demonstrated that this process took place at rather low temperatures (100—400 °C) and was accompanied by complete elimination of the CO groups followed by elimination of the Cp groups. At any metal to chalcogen ratio, the resulting inorganic chalcogenides contained no impurities of metal oxides and carbides. 相似文献
114.
115.
116.
Alenka Turi?nik 《Journal of fluorine chemistry》2003,121(2):245-251
[Mg(HF)2](SbF6)2 and [Ca(HF)2](SbF6)2 monocrystals were grown from the corresponding hexafluoroantimonates(V) dissolved in anhydrous hydrogen fluoride. [Mg(HF)2](SbF6)2 crystallizes in the space group Pnma (no. 62) with a=1249.1(4) pm, b=1230.2(4) pm, c=699.1(2) pm, V=1.0742(6) nm3, Z=4. Magnesium is octahedrally coordinated by six fluorine atoms from which two belong to two HF molecules. The structure can be represented by alternating rows of magnesium and antimony atoms running parallel to the c-axis. Magnesium atoms are connected by cis bridging Sb(2)F6 units along the a-axis and by trans bridging Sb(1)F6 units along the b-axis. In this way a three-dimensional network is formed.[Ca(HF)2](SbF6)2 crystallizes in the space group P21/n (no. 14) with a=935.2(3) pm, b=1088.7(3) pm, c=1104.8(3) pm, β=106.697(5)°, V=1.0774(5) nm3, Z=4. The coordination sphere around the calcium atom consists of eight fluorine atoms which define the vertices of an Archimedean antiprism. The two HF molecules directly coordinate the calcium atom and their fluorine atoms are placed in the corners of different square faces of the Archimedean antiprism. The Ca-F(HF) distances are shorter than the Ca-F(Sb) distances. The Sb(1)F6 and Sb(2)F6 groups have four equatorial bridging fluorine atoms, while the Sb(3)F6 groups have only two bridging trans F ligands. The Ca atoms in the [−1,0,1] plane are connected by equatorial F ligands of Sb(1)F6 and Sb(2)F6 units, forming a [Ca(SbF6)+]n layer. These layers are connected by trans bridging Sb(3)F6 groups. HF molecules occupy the space between these layers and additionally contribute to the connection between the layers by hydrogen bonding. 相似文献
117.
Smaragda Grammenudi Marlene Franke Fritz Vögtle Eberhard Steckhan 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):695-707
The tris-bipyridine ligand3a and its stoichiometric Rh3+ complex have been prepared. Cyclovoltammograms of the complex at pH 7.4 using a glassy carbon disk electrode reveal a strong reduction peak at –620 mV and two weak reduction peaks at more negative voltage. The reduction potential of the new complex is shifted by 300 mV to more positive values as compared to [Rh(bipy)3]3+. There is no reversible reoxidation peak of the Rh(I) complex formed due to the decomplexation of one of the three bipyridine units in the course of the transition Rh(III)Rh(I). The Rh(III) complex of3a was also studied with respect to its function as a possible redox mediator for the electrochemical regeneration of NADH from NAD+. The preparative electrolysis of the Rh3+ complex of3a in the presence of NAD+ yields a selective formation of NADH, whereas NAD dimers were not detected. On the other hand, a significant acceleration of this reaction compared to [Rh(bipy)3]3+ was not observed. 相似文献
118.
Nano-sized phosphine and pyridine ligands having tetraphenylphenyl-, m-terphenyl-, poly(benzylether) moieties were synthesized. These ligands showed a remarkable effect on homogeneous transition
metal catalyzed reactions. Pd(II) complexes with tetraphenylphenyl substituted pyridine ligands show high catalytic activities
for oxidation of ketones suppressing Pd black formation and maintains the catalytic activity for a long time. Rh(I) complex
catalysts with m-terphenyl substituted phosphine ligands showed remarkable rate acceleration in the hydrosilylation of ketones. In addition,
several phosphinocalixarene ligands were synthesized and their coordination studies with Pd(II), Pt(II), Ru(II), Ir(I), and
Rh(I) metals were documented. Ir(I) and Rh(I) cationic complexes with a 1,3,5-triphosphinocalix[6]arene ligand showed dynamic
behavior with size-selective molecular recognition. 相似文献
119.
del Mar Conejo M Fernández R del Río D Carmona E Monge A Ruiz C Márquez AM Sanz JF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4452-4461
The beryllocenes [Be(C(5)Me(4)H)(2)] (1), [Be(C(5)Me(5))(2)] (2), and [Be(C(5)Me(5))(C(5)Me(4)H)] (3) have been prepared from BeCl(2) and the appropriate KCp' reagent in toluene/diethyl ether solvent mixtures. The synthesis of 1 is facile (20 degrees C, overnight), but generation of decamethylberyllocene 2 demands high temperatures (ca. 115 degrees C) and extended reaction times (3-4 days). The mixed-ring beryllocene 3 is obtained when the known [(eta(5)-C(5)Me(5))BeCl] is allowed to react with K[C(5)Me(4)H], once more under somewhat forcing conditions (115 degrees C, 36 h). The structures of the three metallocenes have been determined by low-temperature X-ray studies. Both 1 and 3 present eta5/eta1 geometries of the slip-sandwich type, whereas 2 exhibits an almost regular, ferrocene-like, sandwich structure. In the mixed-ring compound 3, C(5)Me(5) is centrally bound to beryllium and the eta(1)-C(5)Me(4)H ring bonds to the metal through the unique CH carbon atom. This is also the binding mode of the eta(1)-ring of 1. To analyze the nature of the bonding in these molecules, theoretical calculations at different levels of theory have been performed on compounds 2 and 3, and a comparison with the bonding in [Be(C(5)H(5))(2)] has been made. As for the latter molecule, energy differences between the eta5/eta5 and the eta5/eta1 structures of 2 are very small, being of the order of a few kcal mol(-1). Constrained space orbital variations (CSOV) calculations show that the covalent character in the bonding is larger for [Be(C(5)Me(5))(2)] than for [Be(C(5)H(5))(2)] due to larger charge delocalization and to increased polarizability of the C(5)Me(5) fragment. 相似文献
120.
[Re(CO)6][BF4] reacts with HMPA to form [Re(CO)3(HMPA)3][BF4] (4), whose structure was determined by X-ray crystallography and proves to be a key intermediate in the ligand exchange reaction between three CO and Cp; and may be related to other cations such as [Re(CO)3(H2O)3]+, [Re(CO)3(CH3CN)3]+, [Re(CO)3(DMSO)3]+, obtained by different ways, and important in the field of organometallic radiopharmaceuticals. 相似文献