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31.
32.
Millar AJ Doonan CJ Smith PD Nemykin VN Basu P Young CG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3255-3267
Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described. 相似文献
33.
34.
Brajagopal Samanta Joy Chakraborty C. R. Choudhury S. K. Dey D. K. Dey S. R. Batten P. Jensen Glenn P. A. Yap Samiran Mitra 《Structural chemistry》2007,18(1):33-41
We have reported herein the synthesis of three new Cu(II) complexes of tri- and tetradentate Schiff base ligands containing
N3 or N4 donor set along with terminal NNN− or SCN− ligands: [L1Cu(NCS)]ClO4 (1), [L2Cu(NCS)2] (2) and [L3Cu(NNN)]ClO4 (3) [L1 = NC5H4C(CH3)=N(CH2)3N=C(CH3)C5H4N, L2= Me2N–(CH2)3–N=C(CH3)C5H4N and L3 = NC5H4CH=N–(CH2)4–N=CHC5H4N]. The complexes have been systematically characterised by elemental, spectroscopic and electrochemical techniques. Antimicrobial
activities of the Schiff base ligands and their metal complexes have been studied using the disc diffusion method on the strains
of Candida tropicalis and Bacillus megaterium. Structures of all the complexes have been unequivocally established from single crystal X-ray diffraction analyses that
show the monomeric units containing a five-coordinated copper center in highly distorted square pyramidal geometry with thiocyanate
or azide anion coordinated as terminal ligand. The complexes 1 and 3 crystallise in monoclinic (P21/c) and 2 in triclinic (P-1) space group, respectively. 相似文献
35.
Graff JN McElhaney AE Basu P Gruhn NE Chang CS Enemark JH 《Inorganic chemistry》2002,41(10):2642-2647
Complexes of the form (Tp*)MoOCl(p-OC(6)H(4)X) and (Tp*)MoO(p-OC(6)H(4)X)(2) (Tp* = hydrotris(3,5-dimethyl-1-pyrazolyl)borate and X = OEt, OMe, Et, Me, H, F, Cl, Br, I, and CN) were examined by electrochemical techniques and gas-phase photoelectron spectroscopy to probe the effect of the remote substituent (X) on electron-transfer reactions at the oxomolybdenum core. Cyclic voltammetry revealed that all of these neutral Mo(V) compounds undergo a quasireversible one-electron oxidation (Mo(VI)/Mo(V)) and a quasireversible one-electron reduction (Mo(V)/Mo(IV)) at potentials that linearly depend on the electronic influence (Hammett sigma(p) parameter) of X. The first ionization energies for (Tp*)MoO(p-OC(6)H(4)X)(2) (X = OEt, OMe, H, F, and CN) were determined by photoelectron spectroscopy. A nearly linear correlation was found for the Mo(VI)/Mo(V) oxidation potentials in solution and the gas-phase ionization energies. Calculated heterogeneous electron-transfer rate constants show a slight systematic dependence on the substituent. 相似文献
36.
Mukherjee PS Konar S Zangrando E Mallah T Ribas J Chaudhuri NR 《Inorganic chemistry》2003,42(8):2695-2703
Two novel inorganic-organic hybrid 3D extended networks of Ni(II) and Mn(II) having molecular formulas [(maleate)(2)Ni(3)(bpe)(4)(H(2)O)(4)](NO(3))(2).H(2)O (1) and [(adipate)Mn(bpe)] (2) (bpe = 1, 2-bis(4-pyridyl)ethane), respectively, have been synthesized and characterized by single-crystal X-ray diffraction studies and low-temperature (300-2 K) magnetic measurements. Compound 1 crystallizes in the monoclinic system, space group C2/c (No. 15), with chemical formula C(56)H(62)N(10)Ni(3)O(19), a = 30.955(4) A, b = 12.705(3) A, c = 17.058(5) A, beta = 117.26(2) degrees, and Z = 4. Compound 2 crystallizes in the triclinic system, space group Ponemacr; (No. 2), with chemical formula C(18)H(20)MnN(2)O(4), a = 8.492(2) A, b = 9.444(2) A, c = 11.533(3) A, alpha = 97.19(1) degrees, beta = 94.64(1) degrees, gamma = 105.02(1) degrees, and Z = 2. The structure determination reveals for both a 3D network. Compound 1 contains two crystallographically independent Ni(II) ions in different octahedral environments. Ni(1) lies on an inversion center, and its coordination environment comprises two chelating maleate anions and two bpe nitrogen donors, while the Ni(2) ion is surrounded by meridionally disposed three bpe N atoms, two water molecules, and one oxygen donor from the dicarboxylate anion. Of the three crystallographic independent bpe ligand, one presents an anti and the others a gauche conformation. The corresponding N-to-N distances are 9.344, 6.543, and 6.187 A. Variable-temperature magnetic susceptibility measurement of the complex reveals the existence of a dominant ferromagnetic interaction within the molecule. Compound 2 is composed of Mn(2) dimer units linked by adipate anions to form corrugated 2D sheets which, on interconnection through bpe (anti conformation, N-to-N distance of 9.391 A), produces an interpenetrated 3D alpha-polonium-related type net. Complex 2 reveals to be antiferromagnetic fitting data using a dimeric Mn(II) model that considers negligible magnetic transmission through the carbon skeleton of adipate and the bpe pathway. 相似文献
37.
Treatment of the ligand 6‐aza‐2‐thiothymine (ATT, HL, 1 ) with palladium chloride in methanol forms the ionic complex [(HL)4Pd]Cl2·8MeOH ( 2 ), while its reaction with palladium iodide in same solvent produces the neutral complex trans‐[(HL)2PdI2]·2MeOH ( 3 ) in high yields. The reaction of 1 with Na2[PdCl4] in the presence of sodium acetate in a molar ratio of 2:1:2 and with platinum(II) chloride in presence of sodium acetate led to the dimer tetranuclear complexes [(L4Pd2)NaCl]2·8MeOH ( 4 ) and [L4Pt2Cl2]·6MeOH·H2O ( 5 ). The latter is the first PtIII complex of the ligand. All complexes were characterized by elemental analyses and IR spectroscopy and the crystal structures of 2 , 3 , 4 and 5 are determined by single‐crystal X‐ray diffraction. Crystal data for 2 at ?80 °C: triclinic space group , a = 1006.6(1), b = 1006.9(1), c = 1158.1(1) pm, α = 85.20(1)°, β = 83.84(1)°, γ = 88.91(1)°, Z = 1, R1 = 0.0278; for 3 at ?80 °C: triclinic space group , a = 490.5(1), b = 977.2(2), c = 1116.8(2) pm, α = 90.26(1)°, β = 102.33(1)°, γ = 96.08(1)°, Z = 1, R1 = 0.0394; for 4 at ?80 °C: orthorhombic space group Ccca, a = 1791.7(2), b = 1874.1(2), c = 2044.0(1) pm, Z = 4, R1 = 0.0341 and for 5 at ?80 °C: monoclinic space group P21/c, a = 1464.3(1), b = 2003.7(1), c = 1368.5(1) pm, β = 95.66(1)°, Z = 4, R1 = 0.0429. 相似文献
38.
Partha Sarathi Das Basudam Adhikari Sukumar Maiti 《Journal of polymer science. Part A, Polymer chemistry》1994,32(1):39-45
Fluorination of low-density polyethylene, polyacetylene, and poly(vinyl alcohol) was carried out using SF6 gas under electric discharge. The polymers were partially fluorinated and the extent of fluorination was more in the case of poly (vinyl alcohol) than the other two polymers. The fluorinated polymers were characterized by elemental analysis (Fluorine), IR, and x-ray diffraction. Optical transparency of the films was also measured. The fluorinated polymers show better solvent resistance and decreased transparency than the virgin polymer. © 1994 John Wiley & Sons, Inc. 相似文献
39.
Joy Chakraborty Brajagopal Samanta Andrei S. Batsanov Joan Ribas M. Salah El Fallah Samiran Mitra 《Structural chemistry》2006,17(4):401-407
A ligand–metal–ligand type co-ordination polymer [Ni (C6H12N4)(NCS)2(H2O)2]
n
has been synthesised under controlled hydrothermal conditions. Here 1,3,5,7-tetraazatricyclo[3.3.1]decane [or hexamethylenetetramine (hmt)] has been used as a μ-(N,N′) bidentate spacer molecule. The prepared polymeric complex has been characterised by elemental and spectral analyses. The structure has been confirmed by a single crystal X-ray diffraction study. Magneto-structural correlation has been drawn from cryomagnetic susceptibility measurements (2–300 K) which unequivocally reflects very weak magnetic spin interactions among the long distant octahedral Ni(II) metal centres mediated by hmt and weak hydrogen bonding interactions between the adjacent zigzag one-dimensional polymeric chains carrying into a two-dimensional infinite polymeric framework. 相似文献
40.
Adiabatic electron affinities, optimized molecular geometries, and IR-active vibrational frequencies have been predicted for small cyclic hydrocarbon radicals C(n)H(2)(n)(-)(1) (n = 3-6) and their perfluoro counterparts C(n)F(2)(n)(-)(1) (n = 3-6). Total energies and optimized geometries of the radicals and corresponding anions have been obtained using carefully calibrated (Chem. Rev. 2002, 102, 231) density functional methods, namely, the B3LYP, BLYP, and BP86 functionals in conjunction with the DZP++ basis set. The predicted electron affinities show that only the cyclopropyl radical tends to bind electrons among the hydrocarbon radicals studied. The trend for the perfluorocarbon (PFC) radicals is quite different. The electron affinities increase with expanding ring size until n = 5 and then slightly decrease at n = 6. Predicted electron affinities of the hydrocarbon radicals using the B3LYP hybrid functional are 0.24 eV (C(3)H(5)/C(3)H(5)(-)), -0.19 eV (C(4)H(7)/C(4)H(7)(-)), -0.15 eV (C(5)H(9)/C(5)H(9)(-)), and -0.11 eV (C(6)H(11)/C(6)H(11)(-)). Analogous electron affinities of the perflurocarbon radicals are 2.81 eV (C(3)F(5)/C(3)F(5)(-)), 3.18 eV (C(4)F(7)/C(4)F(7)(-)), 3.34 eV (C(5)F(9)/C(5)F(9)(-)), and 3.21 eV (C(6)F(11)/C(6)F(11)(-)). 相似文献