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Treatment of an acetonitrile solution of CuI with 1, 10‐dithia‐18‐crown‐6 (1, 10DT18C6) in the presence of Rb2CO3 leads to formation of the lamellar coordination polymer [Rb{Cu4I5(1, 10DT18C6)2}] ( 1 ).The anionic network of 1 is composed of parallel [(Cu4I5)—] chains linked by bridging thiacrown ether ligands, pairs of which coordinate the Rb+ counter cations. [Cs{Cu5I6(1, 10DT18C6)2}] ( 2 ) can be prepared under similar conditions but contains separated helical anionic chains. In this case 1, 10DT18C6 ligands bridge copper atoms of individual chains in an intrastrand manner. In contrast the coordination networks in [(CuCN)2(1, 10DT18C6)] ( 3 ) and [K2{Cu12(CN)14(1, 10DT18C6)3} · CH3CN] ( 4 ) are both three‐dimensional and based on CuCN‐containing sheets bridged by 1, 10DT18C6 ligands. In the latter compound pairs of K+ cations are coordinated by groups of three thiacrown ether molecules. The neutral network of 3 can imbibe up to 31 % KNO3 per 1, 10DT18C6 pair without loss of lattice integrity. 相似文献
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Treatment of an acetonitrile solution of CuI with 1, 7‐dithia‐18‐crown‐6 (1, 7‐DT18C6) at 100°C affords the coordination polymer 1[(CuI)2(1, 7‐DT18C6)2] ( 1 ) in which 1, 7‐DT18C6 ligands bridge (CuI)2 rings into double chains. 1D polymers of the type 1[M{(Cu3I4)(1, 7‐DT18C6)}] (M = K, 2 ; M = Cs, 3 ) can be isolated under similar conditions in the presence of respectively KI and CsI. Both contain bridging heptacyclic [Cu6I8]2— units but crystallise in different space groups, namely P1 and C2/m. The cesium cation of 3 is markedly displaced from the best plane through the thiacrown ether donor atoms. Reaction of 1, 7‐DT18C6 with CuSCN in the presence of NaSCN yields 2[{Na(CH3CN)2} {(CuSCN)2(1, 7‐DT18C6)}][Cu(SCN)2] ( 4 ), in which 1[(CuSCN)2] double chains are linked through macrocycles into sheets. Infinite 1[{Cu(SCN)2}—] chains compensate the charge of the Na+ cations. Complex 1 can imbibe 0.90 mol CsNO3 per mol of 1, 7‐DT18C6 pairs. 相似文献
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Syntheses, Single-Crystal X-Ray Analyses and Solid-State 29Si NMR Studies of a Zwitterionic λ5-Spirosilicate and a Cage-like Octa(silasesquioxane) The zwitterionic λ5-spirosilicate bis[2,3-naphthalenediolato(2 ?)][2-(dimethylammonio)phenyl]silicate ( 1 ; isolated as 1 · 1/2 CH3CN) was synthesized by reaction of the [2-(dimethylamino)phenyl]dimethoxyorganosilanes 5, 6 and 7 [2-(Me2N)C6H4Si(OMe)2R: R = Ph ( 5 ), cyclo? C6H11 ( 6 ), Me ( 7 )] with 2,3-dihydroxynaphthalene in acetonitrile at room temperature. Reaction of 1 · 1/2 CH3CN or [2-(dimethylamino)phenyl]trimethoxysilane ( 3 ) with water in acetonitrile yielded the cage-like octa{[2-(dimethylamino)phenyl]silasesquioxane} ( 2 ). The crystal structures of 1 · 1/2 CH3CN and 2 were studied by X-ray diffraction. In addition, 1 · 1/2 CH3CN and 2 were characterized by solid-state (29Si CP/MAS) and solution NMR studies (1H, 13C, 29Si). 相似文献
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On the Alkali Selenoarsenates(III) KAsSe3 · H2O, RbAsSe3 · 1/2 H2O, and CsAsSe3 · 1/2 H2O The alkali selenoarsenates(III) KAsSe3 · H2O, RbAsSe3 · 1/2 H2O, and CsAsSe3 · 1/2 H2O have been prepared by hydrothermal reaction of the respective alkali carbonate with As2Se3 at a temperature of 135°C. Their X-ray structural analyses demonstrated that the compounds contain polyselenoarsenate(III) anions (AsSe3?)n, in wich the basic units are ψ-AsSe3 tetrahedra, which are linked together through Se? Se bonds into infinite zweier single chains. The Rb and Cs salts are isotypic. 相似文献
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Hydrothermal reaction of [MnCl2(terpy)] with elemental As and Se at 150 °C in 1:2:4 and 1:4:8 molar ratios in the presence of Cs2CO3 affords the complexes [{Mn(terpy)}2 (As2Se5)]2 ( 1 ) and [{Mn(terpy)}2 (As4Se8)] ( 2 ), respectively. 1 contains dipyramidal [As2Se5]4? ligands that bridge three MnII atoms in a tetradentate μ3‐1κ2Se1,Se2:2κSe4:3κSe5 manner. The tetranuclear complex is centrosymmetric and exhibits a central 8‐membered (MnSeAsSe)2 ring. Cyclic [As4Se8]4? ligands are present in the centrosymmetric dinuclear complex 2 and chelate the Mn(II) atoms through adjacent terminal Se atoms. Both 1 and 2 are linked into infinite chains through weak Mn···Se interactions. [{Mn(terpy)}2(As4S8)] ( 3 ) and ( 4 ) can be obtained by hydrothermal reaction of [MnCl2(terpy)] with As2S3 at respectively 150 °C and 190 °C. Whereas 3 exhibits an identical connectivity pattern to that of 2 , the coordination polymer 4 contains vierer chains that coordinate {(terpy)Mn}2+ fragments in a bidentate manner through terminal S atoms. The complex ( 5 ) contains double chains and results from the analogous hydrothermal reaction of [MnCl2(tren)] with As2S3 at 150 °C. 相似文献
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