全文获取类型
收费全文 | 41061篇 |
免费 | 4251篇 |
国内免费 | 7267篇 |
专业分类
化学 | 35135篇 |
晶体学 | 1912篇 |
力学 | 2261篇 |
综合类 | 317篇 |
数学 | 2242篇 |
物理学 | 10712篇 |
出版年
2024年 | 94篇 |
2023年 | 368篇 |
2022年 | 800篇 |
2021年 | 847篇 |
2020年 | 1175篇 |
2019年 | 1067篇 |
2018年 | 938篇 |
2017年 | 1125篇 |
2016年 | 1571篇 |
2015年 | 1516篇 |
2014年 | 1849篇 |
2013年 | 2933篇 |
2012年 | 3371篇 |
2011年 | 2345篇 |
2010年 | 2006篇 |
2009年 | 2500篇 |
2008年 | 2682篇 |
2007年 | 2787篇 |
2006年 | 2596篇 |
2005年 | 2387篇 |
2004年 | 2353篇 |
2003年 | 2005篇 |
2002年 | 2148篇 |
2001年 | 1365篇 |
2000年 | 1405篇 |
1999年 | 1123篇 |
1998年 | 993篇 |
1997年 | 810篇 |
1996年 | 808篇 |
1995年 | 719篇 |
1994年 | 680篇 |
1993年 | 514篇 |
1992年 | 535篇 |
1991年 | 316篇 |
1990年 | 260篇 |
1989年 | 199篇 |
1988年 | 194篇 |
1987年 | 134篇 |
1986年 | 123篇 |
1985年 | 133篇 |
1984年 | 108篇 |
1983年 | 86篇 |
1982年 | 81篇 |
1981年 | 74篇 |
1980年 | 71篇 |
1979年 | 72篇 |
1978年 | 54篇 |
1977年 | 56篇 |
1974年 | 43篇 |
1973年 | 50篇 |
排序方式: 共有10000条查询结果,搜索用时 218 毫秒
961.
Synthesis and Crystal Structure of Hydronium-tris-ethylenediamine-cobalt(rhodium)-μ-trichloro-nonachlorotrirhenate(III)-chloride, H3O[MEn3][Re3Cl12]Cl (M=Co, Rh) The chlorides H3O[MEn3][Re3Cl12]CI (M = Co, 1 ; Rh, 2 ) crystallize from hydrochloric acid solutions of ReCl3 and MEn3 · 3H2O as deep red hexagonal columns. They are isotypic and crystallize with the hexagonal system (P6 , Z = 1; 1: a = 1010.87(3); c = 794.30(4) pm, R = 0.023, Rw = 0.016; 2: a = 1018.58(3); c = 794.74(4) pm, R = 0.026, Rw = 0.018). The anions [Re3Cl12]3? are connected via H3O+ cation (C.N. 3). The large channels that run in the [001] direction contain, alternatively, the cations [MEn3]3+ and the lonesome Cl?-anions 相似文献
962.
Preparation and Crystal Structure of LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) and Thermal Decomposition to LnBr3 LnAl3Br12 (Ln = La, Ce, Pr, Nd, Sm, Gd) was prepared in crystalline form for the first time. The crystal structures of LaAl3Br12, PrAl3Br12, and NdAl3Br12 were determined on single crystals by X-ray methods. The isotypic compounds crystallize with trigonal symmetry, space group P 3112, Z = 3. A structural comparison to lanthanoide chloroaluminates of equal composition is given and thermal decomposition of LnAl3Br12 (Ln = Nd) to the corresponding lanthanoide tribromide is described. 相似文献
963.
1INTRoDUCTIoNIntenseinterestintransition-metalclusterscontinuesbecausetheyrepresentpos-sibleconceptualbridgesbetweenhomogeneousandheterogeneouscatalystsmoreoveralsobecausetheyrepresentsyntheticchallenges.TheuseofelementsofGroup16ofthePeriodicTableassingleatomligandsforclustergrowthandstabilizationofthemetalcorearenowwellestablished[1i.ThereisanincreasinginterestintheuseofSe-bridgrdclusters,manyofthereactionsofSe2Fe2(CO),andSe2Fe,(CO),havebeenreported"';however,therehasbeenverylittlewor… 相似文献
964.
A. V. Garbar M. R. Leonov L. N. Zakharov Yu. T. Struchkov 《Russian Chemical Bulletin》1996,45(2):451-454
A new neutral -arene complex of trivalent uranium, (6-C6H5Me)U(AlCl4)3 (1), was obtained by the reductive Freidel-Crafts reaction. The crystal structure of 1 was determined by single crystal X-ray diffraction analysis. The U atom in 1 is bound to the C6H5Me group by the 6 mechanism and is linked to the three AICl4 groups through two g-CI bridges. The coordination of the U atom is a distorted pentagonal bipyramid in which the center of the arene ring is in one apical position, and the bridging Cl atoms occupy the other vertices.Translated from Izvestiva Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 469–472, February, 1996. 相似文献
965.
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
966.
W. Mikenda F. Pertlik E. Steinwender 《Monatshefte für Chemie / Chemical Monthly》1993,124(8-9):867-875
Summary X-ray structural data are reported for 2-hydroxy-benzhydrazide(monoclinic; P21/n-C
2h
5
;a=10.569(2) Å,b=11.264(2) Å,c=6.074(1) Å, =98.80(1)°;Z=4;R=0.054) and 2-hydroxy-thiobenzhydrazide (monoclinic; P21/n-C
2h
5
;a=14.598(6) Å,b=5.975(2) Å,c=9.286(4) Å, =107.80(3)°;Z=4;R=0.044). In both compounds the phenolic OH groups are intramolecularly hydrogen bonded to the (thio)carbonyl oxygens and sulfurs, respectively; the basic intermolecular association patterns consist of closed six-membered hydrogen bonded dimers which are connected via N-H ... NH2 hydrogen bonds. The spectral characteristics of the intramolecular O-H...O/S hydrogen bonds (solid state
(OH)=2800/2700 cm–1, CCl4 solution
(OH)=3035/3100 cm–1, CDCl3 solution (OH)=11.62/10.56 ppm) are similar to those of corresponding primary and secondary amides. The solid state IR spectra are consistent with hydrogen bonded NH groups and free NH2 groups, the solution IR spectra indicate free NH2 as well as free NH groups.
Wasserstoffbrückenbindung in 2-Hydroxy-benzhydrazid und 2-Hydroxy-thiobenzhydrazid. Strukturelle und spektroskopische Untersuchungen
Zusammenfassung Es werden Röntgenstrukturdaten für 2-Hydroxy-benzhydrazid (monoklin; P21/n- C 2h 5 ;a=10.569(2) Å,b=11.264(2)Å,c=6.074(1)Å, =98.80(1)°;Z=4;R=0.054) und 2-Hydroxy-thiobenzhydrazid (monoklin; P21/n - C 2h 5 ;a=14.598(6)Å,b=5.975(2)Å,c=9.286(4)Å, =107.80(3)°;Z=4;R=0.044) berichtet. In beiden Verbindungen bilden die phenolischen OH-Gruppen intramolekulare Wasserstoffbrücken mit den Carbonyl-Sauerstoff-, bzw. den Thiocarbonyl-Schwefel-Atomen. Das intermolekulare Assoziationsmuster wird durch N-H...NH2 Wasserstoffbrücken bestimmt, die jeweils zwei Moleküle über sechszählige Ringe zu Dimeren verbinden. Die IR- und NMR-spektroskopischen Charakteristika der intramolekularen O-H...O/S Wasserstoffbrücken (kristallin: (OH)=2800/2700 cm–1, CCl4-Lösungen: (OH)=3035/3100 cm–1, CDCl3-Lösungen: (OH)=11.62/10.56 ppm) sind sehr ähnlich zu denen entsprechender primärer und sekundärer Amide. Die Festkörper-IR-Spektren stehen in Einklang mit assoziierten NH- und freien NH2-Gruppen, während die Lösungs-IR-Spektren auch auf das Vorliegen freier NH-Gruppen schließen lassen.相似文献
967.
Nigel T. Lucas Marie P. Cifuentes Lam T. Nguyen Mark G. Humphrey 《Journal of Cluster Science》2001,12(1):201-221
The new phosphines Ph2PC6H4-4-CCR [R=SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-CCSiMe3)3 (4) and Ru(CCC6H4-4-PPh2)(PPh3)2(-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-CCH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(-C5H5)]PF6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-CC)Ru(PPh3)2(-C5H5)}3 (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) Å3, Z=2, R=0.078, Rw=0.105 for 5008 reflections [I>2.00(I)]. 相似文献
968.
The thermal reaction between the tris(μ-hydrido)dodecacarbonyltrirhenium (o) cluster and triphenylphosphine or triphenylphosphite results in a trisubstituted rhenium cluster as the major product. The results of an X-ray structural analysis of H3Re2(CO)9(PPh3) are: Mr=1597.57, Monoclinic, P21/n, a=15.598(1), b=9.530(2), c=41.685(3) Å, β=80.60(1)°, V=6113.(1) Å3, Z=4, Dc=1.736 g/cm3, CuKe, λ-1.54056 Å, μ-121.23 cm?1, F(000)=3059.17, room temperature, R=0.049 for 7361 reflections with I≥2.5σ(I). The molecule has a triangular Re2 core coordinated propellerwise by three PPh3 ligands in the molecular plane with virtual C3k symmetry. 相似文献
969.
1 INTRODUCTION Tri-butyl phosphate (TBP) has been widely used as the extraction reagent in U-Th fuel to separate uranium from thorium. But di-butyl phos- phate (DBP) and butyl phosphate (MBP), the radio- lytic products of TBP, exhibit some coordinated ability to the fission elements, such as Zr and Nb. The substitutes for TBP have being studied for several decades[1~4]. The physical and chemical properties of amides are similar to those of TBP and they selectively extract U(Ⅵ… 相似文献
970.
Lj.?Radonji 《Journal of Thermal Analysis and Calorimetry》2005,79(3):487-492
Summary The subject of this study was to investigate the effect of fluoride ions addition on the temperature of sol gel mullite formation based on the hypotheses that the presence of fluoride ions can decrease the temperature of mullite formation (in respect to common 980°C, in sol-gel processing). Polymeric sols were prepared by mixing TEOS and aluminum nitrate nanohydrate and by adding fluoride ions (from 2 to 5 mass%). DTA, TG, XRD and SEM were used for characterisation of mullite gel and crystalline mullite. The experimental results confirmed that the addition of fluoride ions decrease the temperature of mullite formation up to 890°C for the fluorine concentration of 3.5 mass%. Experimental results showed that the temperature of mullite formation is not a simple function of the fluoride ion content. The mechanism of fluorine effect was discussed in terms of the gelling process, gel structure and the phase separation before the mullite formation. 相似文献