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121.
Liliana Craciun 《Tetrahedron letters》2004,45(25):4985-4987
1-(o-Carboran-9-yl)-2,3,4,5,6-pentaphenylbenzene (1) was prepared by the Diels-Alder reaction of 9-phenylethynyl-o-carborane and tetraphenylcyclopentadienone at 300 °C. An X-ray crystal structure of 1 shows that the steric demands of the carborane induce a significant stretching of the aryl carbon-boron bond as well as a variety of distortions of the central benzene ring, the ortho phenyl groups, and the carborane cage. 相似文献
122.
123.
Xin Jin Shiyan Guo Dr. Xueli Wang Dr. Muyu Cong Prof. Jinquan Chen Prof. Zhiyun Zhang Prof. Jianhua Su Prof. Da-Hui Qu Prof. He Tian 《Angewandte Chemie (International ed. in English)》2023,62(29):e202305572
We demonstrate that a single polycyclic π-scaffold can undergo sequential multistep excited-state structural evolution along the bent, planar, and twisted conformers, which coexist to produce intrinsic multiple fluorescence emissions in room-temperature solution. By installing a methyl or trifluoromethyl group on the ortho-site of N,N′-diphenyl-dihydrodibenzo[a,c]phenazine ( DPAC ), the enhanced steric effects change the fluorescence emission of DPAC from a dominant red band to well-resolved triple bands. The ultra-broadband triple emissions of ortho-substituted DPAC s range from ≈350 to ≈850 nm, which is unprecedented for small fluorophores with molecular weight of <500. Ultrafast spectroscopy and theoretical calculations clearly reveal that the above dramatic changes originate from the influence of steric hindrance on the shape of excited state potential energy surface (S1 PES). Compared to the steep S1 PES of parental DPAC , the introduction of ortho-substituent is shown to make the path of structural evolution in S1 wider and flatter, so the ortho-substituted derivatives exhibit slower structural transformations from bent to planar and then to twisted forms, yielding intrinsic triple emission. The results provide the proof of concept that the bent, planar, and twisted emissive states can coexist in the same S1 PES, which greatly expand the fundamental understanding of the excited-state structural relaxation. 相似文献
124.
A novel trifunctional initiator with one alkyne and two trifluoromethanesulfonate moieties was synthesized from a protected alcohol 5-hydroxyl-2-phenyl-1, 3-dioxane. The alkyne functionalized intermediate with two protected alcohol groups was synthesized by reacting with propargyl bromide. The alcohol groups were cleaved using a mixture of tetrahydrofuran and hydrochloric acid aqueous solution. In the last step the initiator was synthesized using triflic anhydride in carbon tetrachloride. The initiator was characterized by 1H NMR and used for the polymerization of 2-ethyl-2-oxazoline which gives polymers with narrow distribution. For comparison a similar initiator with two tosylates was prepared and used for the polymerization of the monomer 2-ethyl-2-oxazoline, the resulting product has a wide molecular weight distribution and most of the initiator remains unreacted after 24 h which may be due to the steric hindrance between the two tosylate groups. To further explore the steric hindrance phenomenon, a linear tosylate initiator was synthesized, but still some of the initiator remains unreacted, illustrating that both steric hindrance and electrophilic balance affect the efficiency of the cationic ring-opening polymerization. All of the polymers were characterized in detail by using 1H NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy, and size exclusion chromatography to confirm the purity and distribution of the polymers. 相似文献
125.
2,3-二氰基-2,3-二(X-取代苯基)丁二酸二乙酯在苯乙烯中的分解动力学研究齐陈泽,吴靖嘉,段大勇,贾志胜,张斌,杨第伦(兰州大学应用有机化学国家重点实验室,兰州大学化学系,兰州,730000)关键词2,3-二氰基-2,3-二(X-取代苯基)丁二... 相似文献
126.
Daniel Polyak Ngan Phung Jian Liu Robert Barrows Thomas J. Emge Spencer Knapp 《Tetrahedron letters》2017,58(40):3879-3883
Homophthalic anhydride (HPA) typically reacts rapidly with benzalimines to afford the formal [4+2] adduct, a 1,2,3,4-tetrahydroisoquinolin-1-one-4-carboxylic acid. The stereochemical outcome of this reaction is consistent with an open transition state comprising an iminium species and enolized HPA, leading to a short-lived amino-anhydride intermediate. In the case of N-tert-butylbenzalimine, this Mannich-type intermediate, which would normally cyclize at low temperature to a single isomer of the delta-lactam, is intercepted by base treatment to afford beta-lactam products. A pathway featuring ketene formation followed by ring closure is implicated. 相似文献
127.
《Journal of Coordination Chemistry》2012,65(21):3718-3728
Three metal complexes with ferrocenecarboxylate ligands, [M2(η 2-FcCOO)2(μ2-η 2-FcCONHCH2COO)2(phen)2]?·?nH2O [M?=?Pb, n?=?6 (1) and M?=?Cd, n?=?2 (2)] and [Cd(FcCONHCH2COO)(μ2-FcCONHCH2COO)(2,2′-bipy)(H2O)] n (3) (FcCOOH?=?ferrocenemonocarboxylic acid, FcCONHCH2COOH?=?N-ferrocenylformylglycine, phen?=?1,10-phenanthroline, 2,2′-biby?=?2,2′-bipyridine), were synthesized and characterized by elemental analysis, IR, and single crystal X-ray diffraction analysis. Structural studies revealed that 1 and 2 have similar binuclear structures, but 3 exhibits a 1-D chain structure. The difference in the structures of ferrocenylcarboxylate-containing cadmium(II) complexes is due to steric hindrance of ferrocenyl groups. 相似文献
128.
Tamim A. Darwish Arthur R.G. SmithIan R. Gentle Paul L. BurnEmily Luks Greta MoraesMarie Gillon Peter J. HoldenMichael James 《Tetrahedron letters》2012,53(8):931-935
Deuterated forms of aromatic charge transporting heterocycles 2 and 3 used in organic light-emitting diodes have been produced by hydrothermal reactions, catalyzed by Pt/C or Pd/C. Comprehensive analysis by mass spectroscopy, 1H, 2H and 13C NMR enables determination of the overall quantity of D atoms present, as well as the level of deuteration at each molecular site. The roles of solubility and steric availability in deuteration are discussed in the light of these results. Neutron reflectometry indicates excellent scattering contrast between protonated and deuterated forms of these molecules, with nanoscale thin films showing the same density as in their bulk molecular forms. Although used for morphological studies of thin films typically used in OLEDs, the synthetic and analysis methods described here are generic and suitable for deuteration of other conjugated aromatic heterocycles and other optoelectronic devices. 相似文献
129.
SENTHILKUMAR Annamalai THARINI Kumaravel SETHURAMAN Mathur Gopalakrishnan 《物理化学学报》2012,28(2):399-406
Three synthesized piperidin-4-one oximes,3-ethyl-2,6-diphenyl-piperidin-4-one oxime(A),1-methyl-3-isopropyl-2,6-diphenyl-piperidin-4-one oxime(B),and 3-isopropyl-2,6-diphenyl-piperidin-4-one oxime(C),were tested at different concentrations to determine their ability to inhibit corrosion of mild steel in 1 mol.L-1 H2SO4 and measured by a mass loss method(at various temperatures),polarization and impedance measurements,X-ray diffraction(XRD),scanning electron microscopy(SEM) with energy-dispersive X-ray spectroscopy(EDS),and a quantum chemical method.The synergistic influence of compounds A,B and C with iodides has also been evaluated.All three compounds show good inhibition efficiency in the following order:A>B>C.Compounds A,B and C were found to physically adsorb on the surface of mild steel while obeying the Temkin isotherm.Polarization measurements indicated that these compounds behave as a mixed mode inhibitor.XRD and SEM with EDS studies revealed the formation of a protective barrier on the mild steel surface by these oximes.The electron donating ability of the studied molecules was tested using semi empirical methods.The studies revealed that the oxime nitrogen,the piperidine moiety,and the phenyl ring assist largely in corrosion control.The studies also showed that the steric crowding by the alkyl group in the piperidine ring affects the inhibitor efficiency.Further,it is interesting to note that all of the studied compounds exhibit synergism with iodide ions. 相似文献
130.
The push,pull effect in two series of disubstituted alkynes was studied at the DFT level [B3LYP/6-311G(d)] by application of the 13C chemical shift differences (GIAO) between the alkyne carbon atoms (ΔδCC), the charge difference between these carbons (ΔqCC), the occupation quotient (NBO) of anti-bonding π∗, and bonding π orbitals (π∗CC/πCC) and the bond length (dCC) of the CC triple bond. The linear dependence of dCC versus π∗CC/πCC quantifies changes in the push,pull effect while deviations from the latter correlation indicate and ascertain quantitatively to what extent steric hindrance restricts the strain-less conjugation of the CC triple bond π-orbitals in the disubstituted alkynes. 相似文献