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101.
Synthesis,Crystal Structure,and Hydrogen Bonding of μ‐Hydroxo‐μ‐peroxo‐bis[bis(ethylenediamine)cobalt(III)] Squarate
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Black‐brown needle‐shaped single crystals of [Co2(en)4(O2)(OH)][C4O4]1.5 · 4H2O (en = ethylenediamine) were prepared in aqueous solution at room temperature [space group P$\bar{1}$ (no.2) with a = 800.20(8), b = 1225.48(7), c = 1403.84(9) pm, α = 100.282(5), β = 94.515(7), and γ = 95.596(6)°]. The Co3+ cations [Co(1), Co(2)] are coordinated in an octahedral manner by four nitrogen atoms stemming from the ethylenediamine molecules and two oxygen atoms each from a hydroxo group and a peroxo group, respectively. Both Co3+ coordination polyhedra are connected by a common corner and by the peroxo group leading to the dinuclear [(en)2Co(O2)(OH)Co(en)2]3+ cation. The squarate dianions, not bonded to Co3+, and the [(en)2Co(O2)(OH)Co(en)2]3+ cations are linked by hydrogen bonds forming a three‐dimensional supramolecular network containing water molecules. Magnetic measurements revealed a diamagnetic behavior indicating a low‐spin electron configuration of Co3+. The UV/Vis spectra show two LMCT bands [π*(O22–) → dσ*(Co3+)] at 274 and 368 nm and the d–d transition (1A1g → 1T1g) at 542 nm. Thermoanalytical investigations in air show that the compound is stable up to 120 °C. Subsequent decomposition processes to cobalt oxide are finished at 460 °C. 相似文献
102.
103.
The reactions of LnCl3·6H2O (Ln=Eu or Dy) and Na2[Mo2O3S(HNTA)2]·6H2O afford Na[Mo2O3S(HNTA)2]2·Eu(H2O)9·3H2O (1) (NTA=nitrilotriacetate) and Na{(H2O)6Dy[Mo2O3S(HNTA)2]2}·7.5H2O (2), respectively. The [Mo2O3S(HNTA)2]2− cluster units of 1 are interconnected by Na+ into a 3-D open framework with rutile topology templated by . The coordination of [Mo2O3S(HNTA)2]2− to the slightly smaller Dy3+ ion of greater ionic potential as a consequence of lanthanide contraction has been observed to form the pentanuclear heterometallic {Dy(H2O)6[Mo2O3S(HNTA)2]2}−, which is linked by Na+ and hydrogen bonds between the protonated carboxylate groups into a 3-D supramolecular framework. The weak antiferromagnetic interactions between the Dy3+ ions of 2 have been observed. 相似文献
104.
Xiao‐Xu Li Ning Wang Shan‐Tang Yue Prof. Dr. Zhao‐Yang Li Hong‐Yan Wu Ying‐Liang Liu 《无机化学与普通化学杂志》2009,635(15):2648-2652
Self‐assembly of the rigid organic ligand 2‐propyl‐4,5‐dicarboxy‐1H‐imidazole ( L ) with different metal ions (Zn2+, Ni2+, Cu2+, Cd2+) led to four new complexes, namely, [M( L )(phen)] [M = Zn ( 1 ); Ni ( 2 ); Cd ( 3 )] and [Cu( L )( 4 )] (phen = 1,10‐phenanthroline). Their structures were determined by single‐crystal X‐ray diffraction analyses, and they were further characterized by elemental analysis, IR spectroscopy, and thermogravimetric analysis. Whereas compounds 1 , 2 , and 3 are discrete units, hydrogen‐bonding interactions play a vital role in these complexes. Compounds 1 and 2 form one‐dimensional (1D) and two‐dimensional (2D) structures through hydrogen‐bondinginteractions with helical character. In 1 , the hydrogen bonds (O–H ··· O) alternately bridge the MII cations of the discrete units to form a one‐dimensional (1D) infinite helical chain. Complex 2 forms a 2D helical layer through parallel hydrogen bonds (N/O–H ··· O/N) between two adjacent helical chains. In 3 , the hydrogen bonds (N–H ··· O) connect adjacent discrete units into a ten‐membered ring with extension into a one‐dimensional double‐chain supramolecular structure. Complex 4 is a two‐dimensional gridlike (4,4) topological layer which is extended to a 3D network by hydrogen bonding. The solid‐state fluorescence spectrum of complex 3 was determined. 相似文献
105.
The synthesis and physical properties of bis(2-(1H-imidazol-2-yl)-pyridine)copper(II) with chloride, nitrate and perchlorate as counteranions have been described. Microanalysis, magnetic susceptibility, conductivity and various spectroscopic measurements have been used for the characterization of the complexes. The crystal structures of all three complexes have been determined. Intermolecular hydrogen-bonding interactions and the resulting self-assembly patterns for each of the species have been scrutinized. The chloride containing complex crystallizes as a trihydrate, where the metal ion is in a tetragonally elongated cis-N4Cl2 coordination sphere. This complex provides a three-dimensional honeycomb-like structure through N–H?Cl, O–H?Cl and O–H?O hydrogen bonds. In the nitrate containing species, one of the two counteranions coordinates to the metal centre to provide an irregular N4O2 coordination sphere, while the other counteranion, with the help of a lattice water molecule, assembles a ladder-like structure via N–H?O and bifurcated O–H?O,O hydrogen bonds. A one-dimensional polymeric species has been formed when perchlorate is the counteranion. Here one of the two perchlorates acts as a bridge between the metal centres that are in tetragonally elongated trans-N4O2 coordination spheres. This polymeric chain, together with the second perchlorate and a water molecule, form a ribbon-like structure due to N–H?O and O–H?O hydrogen bonds. 相似文献
106.
107.
The reactions of the polydentate ligand 1,4-bis(4,5-dihydro-2-oxazolyl)benzene (L) with AgX (X = CH3COO−, ClO4− and CF3SO3−) afforded the complexes [Ag2(L)(CH3COO)2]∞ (1), [Ag2(L)3(ClO4)2]∞ (2), and [Ag(L)(CF3SO3)]∞ (3), whereas the reaction of L with Ag2SO4 in MeOH/H2O system afforded {[Ag2(L)3(H2O)3][SO4] · 9H2O}∞ (4). The EA and IR have been recorded and all the complexes have been structurally characterized by X-ray crystallography, confirming that complexes 1–4 are two-dimensional coordination polymeric frameworks. The bidentate L ligands in complexes 3 and 4 adopt both the syn and anti conformation and those in 1 and 2 adopt the anti conformation only. The anions CH3CO2− in complex 1 bridge the Ag(I) atoms in η1, η2, μ3-coordination mode forming a 1-D zig-zag –[Ag(CH3COO)]n– chains, while the anions ClO4−, CF3SO3− and SO42− in complexes 2–4 are not coordinated to the Ag(I) atoms, but all of them play an important roles in linking cationic 2-D frameworks into 3-D supramolecular structures. 相似文献
108.
First examples of transition metal complexes with HpicOH [Cu(picOH)2(H2O)2] ( 1 ), [Cu(picO)(2,2′‐bpy)]·2H2O ( 2 ), [Cu(picO)(4,4′‐bpy)0.5(H2O)]n ( 3 ), and [Cu(picO)(bpe)0.5(H2O)]n ( 4 ) (HpicOH = 6‐hydroxy‐picolinic acid; 2,2′‐bpy = 2,2′‐bipyridine; 4,4′‐bpy = 4,4′‐bipyridine; bpe = 1,2‐bis(4‐pyridyl)ethane) have been synthesized and characterized by single‐crystal X‐ray diffraction. The results show that HpicOH ligand can be in the enol or ketonic form, and adopts different coordination modes under different pH value of the reaction mixture. In complex 1 , HpicOH ligand is in the enol form and adopts a bidentate mode. While in complexes 2 – 4 , as the pH rises, HpicOH ligand becomes in the ketonic form and adopts a tridentate mode. The coordination modes in complexes 1 – 4 have not been reported before. Because of the introduction of the terminal ligands 2,2′‐bpy, complex 2 is of binuclear species; whereas in complexes 3 and 4 , picO ligands together with bridging ligands 4,4′‐bpy and bpe connect CuII ions to form 2D nets with (123)2(12)3 topology. 相似文献
109.
Two novel organic-inorganic hybrid compounds based on organoamines and polyoxovanadates formulated as (H2dien)4[H10V18O42(PO4)](PO4)·2H2O (1) (dien=diethylenetriamine) and (Him)8[HV18O42(PO4)] (2) (im=imidazole) have been prepared under hydrothermal conditions by using different starting materials, and characterized by elemental analyses, IR, ESR, XPS, TGA and single-crystal X-ray diffraction analyses. Crystal data for compound 1: C16H74N12O52V18P2, Monoclinic, space group C2/c, a=23.9593(4) Å, b=13.0098(2) Å, c=20.1703(4) Å, β=105.566(3)°, V=6056.6(19) Å3, Z=4; for compound 2, C24H41N16O46V18P, Tetragonal, space group I4/mmm, a=13.5154(8) Å, b=13.5154(8) Å, c=19.1136 Å, β=90°, V=3491.4(3) Å3, Z=2. Compound 1 consists of protonated diens together with polyoxovanadates [H10V18O42(PO4)]5−. Compound 2 is composed of protonated ims and polyoxovanadates [HV18O42(PO4)]8−. There are hydrogen-bonding interactions between polyoxovanadates and different organoamines in 1 and 2. Polyoxovanadates are linked through H2dien into a three-dimensional network via hydrogen bonds in 1, while polyoxovanadates are linked by Him into a two-dimensional layer network via hydrogen bonds in 2. The crystal packing patterns of the two compounds reveal various supramolecular frameworks. 相似文献
110.
Smart strategies that can decrease the side effect and enhance the therapeutic efficacy of chemotherapy are in urgent need to meet the special demands of cance r therapy.Herein,two wate r-soluble macrocyclic hosts,i.e.,a carboxylated leaning tower[6]arene(CLT6) and a carboxylated [2]biphenyl-extended pillar[6]arene(CBpP6),are used to load chemotherapy drug oxaliplatin(OxPt) by forming inclusion complexes(OxPt■CLT6 and OxPt■CBpP6) through host-guest interactions.Interestingly,OxPt can be released from the macrocyclic cavities of these drug delivery systems(DDSs) via the competitive binding effect of spermine(SPM) because of the stronger binding abilities of CLT6/CBpP6 toward SPM as compared with OxPt,leading to enhanced cytotoxicity on SPM-overexpressed cancer cells,such as breast cancer MCF-7 cells.Moreover,compared to free OxPt,due to the low concentration of SPM in normal cells,OxPt■CGT6 and OxPt■CBpP6 demonstrated a decreased cytotoxicity on liver L02 cells,which is beneficial fo r reducing the side effect of anticancer drug during chemotherapy.Such a strategy might be extended to other antitumor drugs and water-soluble macrocycles with suitable cavity sizes to achieve controllable drug delivery and enhanced anticancer ability in supramolecular chemotherapy 相似文献