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991.
M. Dolores Santana Gabriel García Consuelo Vicente-Hernndez Luís García Jos Prez Tefilo Rojo Luís Lezama 《Journal of organometallic chemistry》2008,693(11):2009-2016
The preparation, spectroscopic characterization and magnetic study of N,N′-bis(substituted-phenyl)oxamidate-bridged nickel(II) dinuclear complexes of formula {[Ni(N3-mc)]2(μ-CONC6H4-X)}(PF6)2 (N3-mc = 2,4,4-trimethyl-1,5,9-triazacyclo-dodec-1-ene (Me3-N3-mc) or 2,4,4,9-tetramethyl-1,5,9-triazacyclododec-1-ene (Me4-N3-mc), X = 2-Cl, 4-Cl, 2-OCH3, 4-OCH3) are reported. These paramagnetic nickel(II) complexes have been characterized by both one- and two-dimensional (COSY) 1H NMR techniques. The COSY spectrum of 5 has allowed to achieve the assignment of the phenyl protons of the N,N′-diphenyloxamidate. The crystal structures of [Ni(Me3-N3-mc)(μ-CONC6H4-4-Cl)]2(PF6)2 (6), [Ni(Me3-N3-mc)(μ-CONC6H4-4-OMe)]2(PF6)2 (8) and [Ni(Me4-N3-mc)(μ-CONC6H4-2-Cl)]2(PF6)2 (9) have been determined and their magnetic properties have been studied. The value of magnetic coupling between the two nickel(II) ions across the oxamidate bridge [J = − 37.6 (6), −39.9 (8) and −39.7 cm−1 (9)] is sensitive to the distortion of the coordination sphere of the metal ions and the topology of the molecular bridge. 相似文献
992.
Thermal, photophysical and magnetic properties of some novel fullerenol–silane adducts are described. Excellent improvement of thermal stability and high char yield due to the presence of silicon is the key feature of these adducts. Highest luminescence quenching due to maximum π–π electronic interactions between phenyl ring and fullerene are observed in the aromatic-silane adducts and the quenching ability of the aromatic ring reduces with further delocalization of the π-electrons as in naphthyl silane. The alkyl vinyl silane, on the other hand, records better fluorescence intensity owing to increase population of the electron density (+I effect) and non-effective charge transfer complex formation between isolated vinylic double bond and fullerene. Emission peak positions of these adducts are comparable to fullerenol because of control derivatization of fullerene ring causing less perturbation of the symmetric π-electronic system. These adducts are paramagnetic in nature with peaks around 3515 G and higher g-values (2.005–2.009) compared to fullerenol (1.985). The fullerenol–silane adducts are synthesized using fullerenol as substrate and different chloro and alkoxy silanes as silylating agents adopting simple nucleophilic displacement and transesterification reactions. All the fullerenol–silane adducts are characterized spectroscopically. 相似文献
993.
Richard E. Sykora Peter Khalifah Zerihun Assefa Richard G. Haire 《Journal of solid state chemistry》2008,181(8):1867-1875
Colorless single crystals of Gd(IO3)3 or pale pink single crystals of Er(IO3)3 have been formed from the reaction of Gd metal with H5IO6 or Er metal with H5IO6 under hydrothermal reaction conditions at 180 °C. The structures of both materials adopt the Bi(IO3)3 structure type. Crystallographic data are (MoKα, λ=0.71073 Å): Gd(IO3)3, monoclinic, space group P21/n, a=8.7615(3) Å, b=5.9081(2) Å, c=15.1232(6) Å, β=96.980(1)°, V=777.03(5) Z=4, R(F)=1.68% for 119 parameters with 1930 reflections with I>2σ(I); Er(IO3)3, monoclinic, space group P21/n, a=8.6885(7) Å, b=5.9538(5) Å, c=14.9664(12) Å, β=97.054(1)°, V=768.4(1) Z=4, R(F)=2.26% for 119 parameters with 1894 reflections with I>2σ(I). In addition to structural studies, Gd(IO3)3, Er(IO3)3, and the isostructural Yb(IO3)3 were also characterized by Raman spectroscopy and magnetic property measurements. The results of the Raman studies indicated that the vibrational profiles are adequately sensitive to distinguish between the structures of the iodates reported here and other lanthanide iodate systems. The magnetic measurements indicate that only in Gd(IO3)3 did the 3+ lanthanide ion exhibit its full 7.9 μB Hund's rule moment; Er3+ and Yb3+ exhibited ground state moments and gap energy scales of 8.3 μB/70 K and 3.8 μB/160 K, respectively. Er(IO3)3 exhibited extremely weak ferromagnetic correlations (+0.4 K), while the magnetic ions in Gd(IO3)3 and Yb(IO3)3 were fully non-interacting within the resolution of our measurements (∼0.2 K). 相似文献
994.
Hassan Hadadzadeh S. Jamil A. Fatemi Seyedeh Raziyeh Hosseinian Hamid Reza Khavasi Rainer Pöttgen 《Polyhedron》2008
The structure, spectroscopy and electrochemical properties of a novel dinuclear copper(II) complex, [{Cu(phen)2}2(μ-CH3COO)][PF6]3 where phen = 1,10-phenanthroline, is reported. The crystal structure contains two independent Cu(II) ions, with different geometry around each copper center, which are bridged by an acetate anion. The acetate-bridged ligand shows a syn–anti coordination mode with a trigonal bipyramidal geometry for the Cu(1) center and a distorted square-based pyramidal geometry for the Cu(2) center. The angular structural index parameter τ for Cu(1) and Cu(2) is 0.9 and 0.33, respectively. The copper(II) atoms display a different geometry with a N4O chromophore group and with Cu–O distances of 1.993(5)–1.996(5) Å and Cu–N distances which vary from 1.980(5) to 2.161(6) Å. The intra Cu…Cu separation is 4.9904(5) Å. The effective magnetic moment (μeff) of the complex was measured by the Evans method. The cyclic voltammogram of [{Cu(phen)2}2(μ-CH3COO)][PF6]3 shows two waves at positive potential which are assigned to the two Cu(II/I) reduction couples. 相似文献
995.
Somnath Roy Tarak Nath Mandal Anil Kumar Barik Samik Gupta Ray J. Butcher Mohamed Salah El Fallah Javier Tercero Susanta Kumar Kar 《Polyhedron》2008
The synthesis and structure of a pyrazole-based orthogonal ferromagnetically coupled tetracopper(II) 2 × 2 homoleptic grid complex [Cu4(PzOAPyz)4(ClO4)2](ClO4)2 · 6H2O (1), formed by the reaction between the ditopic ligand PzOAPyz and Cu(ClO4)2 · 6H2O, are described. The ligand contains terminal pyrazole and pyrazine residues bound to a central flexible diazine subunit (N–N) as well as one potentially bridging alkoxo group. The two adjacent metal centers are linked by an alkoxo oxygen forming essentially a square Cu4(μ-O4) cluster. In the Cu4(μ-O4) core, out of the four copper centers, two copper centers are penta-coordinated and the remaining two are hexa-coordinated. In each case of hexa-coordination, the sixth position is occupied by one of the oxygen atoms of a coordinated perchlorate ion. Complex 1 has been characterized structurally and magnetically. Although the large Cu–O–Cu bridge angles (137–138°) and short Cu–Cu distances (3.964–3.970 Å) are suitable for the transmission of the expected antiferromagnetic coupling, the square-based Cu4(μ-O4) cluster exhibits an intramolecular ferromagnetic exchange (J = 7.47 cm−1) between the metal centers with an S = 2 magnetic ground state associated with the quasi orthogonal arrangement of the magnetic orbitals (dx2-y2). The exchange pathway parameters have been evaluated from density functional calculations. 相似文献
996.
997.
Monodispersed Fe3O4/polypyrrole (PPy) hollow particles were synthesized via controllable in-situ deposition and polymerization techniques using poly(styrene-co-acrylic) (PSA) latex as template. Field-dependent magnetization plot illustrates that the capsules are superparamagnetic at 300 K. FTIR spectrum confirms that the myoglobin (Mb) molecule adsorbed on the surface of Fe3O4/PPy hollow particle essentially retains its native structure. Furthermore, direct electrochemistry of Mb can be realized on Fe3O4/PPy capsules modified pyrolytic graphite disk electrode, which indicates that the magnetic conductive polymer capsules can promote the electron transfer of protein. 相似文献
998.
Éadaoin McCourt Dr. Kane Esien Li Zhenyu Dr. Solveig Felton Dr. Peter Nockemann 《Angewandte Chemie (International ed. in English)》2023,62(7):e201809334
Herein, we report on the preparation of liquid dimeric lanthanide(III)-containing compounds. Starting from the design of dimeric solids, we demonstrate that by tuning of anion and cation structures we can lower the melting points below room temperature, whilst maintaining the dimeric structure. Magnetic measurements could establish the spin-spin interactions of the neighboring lanthanide(III) ions in the liquid state at low temperatures, and matched the interactions of the analogous crystalline solid compounds. 相似文献
999.
Anna G. Scott Diogo Alves Galico Isabel Bogacz Paul H. Oyala Junko Yano Elizaveta A. Suturina Muralee Murugesu Theodor Agapie 《Angewandte Chemie (International ed. in English)》2023,62(49):e202313880
Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*4W4Fe13S12 , displaying a Fe13 core with M−M bonds that has precedent only in main group and late metal chemistry. M13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*4W4Fe13S12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements. 相似文献
1000.
Sterically bulky pyrazines have been successfully utilized for the preparation of discrete oligo-nuclear TBP (trigonal bipyramidal), SqP (square pyramidal), and Oh (octahedral) copper(II) complexes. We have synthesized a unique linear pentanuclear complex [{Cu(hfac)2}5(μ-2-butyl-3-methylpyrazine)4]. The two terminal copper(II) ions have a SqP structure while the three inner ions have an Oh one. The solvent molecule was incorporated in the clearance of the lattice. From another reaction under harsh conditions, we separated [{Cu(hfac)2}3(μ-2-butyl-3-methylpyrazine)2], which can be regarded as the central moiety of the pentanuclear one. We also prepared a dinuclear complex [{Cu(hfac)2}2(μ-tetramethylpyrazine)], in which the pyrazine nitrogen atoms were located at TBP equatorial positions. Single-crystal EPR measurements supported its compressed TBP structure. The exchange coupling was antiferromagnetic with JTBP–TBP/kB = −3.6 K. The linear trinuclear [{Cu(hfac)2}3(μ-2,3,5-trimethylpyrazine)2], having two TBP Cu ions with an intervening Oh Cu ion, showed very weak antiferromagnetic coupling. DFT calculations on these compounds indicated that the σ-type orbital overlap between the Cu and N atoms is essential for superexchange interactions. 相似文献