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1.
Motoko S. Asano Sho Hashimoto Takuya Shinozuka Yasutaka Fushimi 《Molecular physics》2019,117(19):2664-2672
ABSTRACTInteraction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent. 相似文献
2.
3.
Proton Order–Disorder Phenomena in a Hydrogen‐Bonded Rhodium–η5‐Semiquinone Complex: A Possible Dielectric Response Mechanism 下载免费PDF全文
Dr. Minoru Mitsumi Kazunari Ezaki Yuuki Komatsu Prof. Dr. Koshiro Toriumi Dr. Tatsuya Miyatou Prof. Dr. Motohiro Mizuno Nobuaki Azuma Prof. Dr. Yuji Miyazaki Prof. Dr. Motohiro Nakano Prof. Dr. Yasutaka Kitagawa Dr. Takayasu Hanashima Dr. Ryoji Kiyanagi Dr. Takashi Ohhara Prof. Dr. Kazuhiro Nakasuji 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9682-9696
A newly synthesized one‐dimensional (1D) hydrogen‐bonded (H‐bonded) rhodium(II)–η5‐semiquinone complex, [Cp*Rh(η5‐p‐HSQ‐Me4)]PF6 ([ 1 ]PF6; Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl; HSQ=semiquinone) exhibits a paraelectric–antiferroelectric second‐order phase transition at 237.1 K. Neutron and X‐ray crystal structure analyses reveal that the H‐bonded proton is disordered over two sites in the room‐temperature (RT) phase. The phase transition would arise from this proton disorder together with rotation or libration of the Cp* ring and PF6? ion. The relative permittivity εb′ along the H‐bonded chains reaches relatively high values (ca., 130) in the RT phase. The temperature dependence of 13C CP/MAS NMR spectra demonstrates that the proton is dynamically disordered in the RT phase and that the proton exchange has already occurred in the low‐temperature (LT) phase. Rate constants for the proton exchange are estimated to be 10?4–10?6 s in the temperature range of 240–270 K. DFT calculations predict that the protonation/deprotonation of [ 1 ]+ leads to interesting hapticity changes of the semiquinone ligand accompanied by reduction/oxidation by the π‐bonded rhodium fragment, producing the stable η6‐hydroquinone complex, [Cp*Rh3+(η6‐p‐H2Q‐Me4)]2+ ([ 2 ]2+), and η4‐benzoquinone complex, [Cp*Rh+(η4‐p‐BQ‐Me4)] ([ 3 ]), respectively. Possible mechanisms leading to the dielectric response are discussed on the basis of the migration of the protonic solitons comprising of [ 2 ]2+ and [ 3 ], which would be generated in the H‐bonded chain. 相似文献
4.
Bo-Hao Chen Jun-Jia Xu Wei-Ren Lai Chung-Kai Chang Jeng-Lung Chen Jyh-Fu Lee Jin-Ming Chen Hwo-Shuenn Sheu Jey-Jau Lee Yoshiki Kubota Ming-Hsi Chiang Yasutaka Kitagawa Yu-Chun Chuang I-Jui Hsu 《中国化学会会志》2023,70(5):1187-1199
Two cobalt(II) halide complexes with 1,2,4-triazole as a ligand were synthesized. Their structures were determined by extended x-ray absorption fine structure (EXAFS) and powder x-ray diffraction (XRD). Both complexes [Co(Htrz)Cl2]n ( 1 ) and {[Co(Htrz)2(trz)]BF4}n ( 2 ) form one-dimensional polymeric chain and the distances of Co⋯Co are 3.3521(2) Å and 3.8629(2) Å, respectively. The Htrz and Cl− are bridging ligands to connect two Co(II) ions in 1 , and the local environment of Co site is in a distorted octahedron with {CoN2Cl4} core. In complex 2 , two Htrz and one trz are bridging ligands to connect two Co(II) ions, and the local geometry of Co is in a pseudo octahedron with {CoN6} core. The analysis of Co LII,III-edge XAS indicates that the Co(II) of both complexes are at high spin state with t2g5eg2 configuration and the crystal field strength (10Dq) is about 1.2 eV. The broken-symmetry DFT calculations indicate that antiferromagnetic coupling state of Co⋯Co is the most stable state in both complexes; and the coupling constants of 1 and 2 are −0.32 cm−1 and −3.70 cm−1, respectively. Based on the distances of Co⋯Co and coupling constants, such antiferromagnetic interaction is achieved through triazole ligands. 相似文献
5.
The purpose of this paper is to estimate the renormalization group theory for turbulence developed by Yakhot and Orszag [J. Sci. Comput. 1 (1986) 3] and reformulated by Yakhot and Smith [J. Sci. Comput. 7 (1992) 35]. We go into details of their basic theory for the Navier-Stokes equations, the transport equations for the turbulent kinetic energy K, and its dissipation rate . As a result, it becomes evident that their theory bears no relationship to Wilson's renormalization group theory for critical phenomena. Their
model is not directly obtained from the renormalization group theory. They evaluated the Kolmogorov constant by setting the expansion parameter ε = 0 and ε = 4 in the same equations. Furthermore, all the constants in their
model are invalid because of the same problem. 相似文献
6.
Dr. Nozomi Mihara Dr. Yasuyuki Yamada Dr. Hikaru Takaya Prof. Yasutaka Kitagawa Dr. Kazunobu Igawa Prof. Katsuhiko Tomooka Prof. Hiroshi Fujii Prof. Kentaro Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(13):3369-3375
Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+, which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H2O2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS4−) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS4− to 3 5+ enhanced the catalytic activity. 相似文献
7.
Yasuhiro Matoba Hiroshi Inoue Jun-Ichi Akagi Takuji Okabayashi Yasutaka Ishii Masaya Ogawa 《合成通讯》2013,43(9):865-873
Applicatims a Mo- and W-based heteropoly acids (HPA) as a catalyst in the oxidation of olefins have extensively been investigated1. However, a patent work is only attempted concerning the evoxidatim of olefins with H202 by HPA2) since the oxirane ring is cleaved because of a strong acidity of HPA itself. Herein, an effective epoxidatim of some allylic alcohols with H202 by a new Mo-species (MPCP), which was prepared from 12-molybdatophosphoric acid (H3PMo12040) and cetylpyridinium chloride (C5H5N (CH2), 15CH3- C1-) under two-phase conditions using chloroform as an organic solvent, is described. 相似文献
8.
Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Haruka Miyano Prof. Dr. Yasuyuki Ura Prof. Dr. Yasutaka Kitagawa Dr. Shiho Yada Prof. Dr. Tomokazu Yoshimura Prof. Dr. Takayuki Nakajima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(47):12078-12103
A series of the octapalladium chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) ligands, [Pd8(meso-dpmppm)4(L)2](BF4)4 (L=none ( 1 ), solvents: CH3CN ( 2 a ), dmf ( 2 b ), dmso ( 2 c ), RN≡C: R=Xyl ( 3 a ), Mes ( 3 b ), Dip ( 3 c ), tBu ( 3 d ), Cy ( 3 e ), CH3(CH2)7 ( 3 f ), CH3(CH2)11 ( 3 g ), CH3(CH2)17 ( 3 h )) and [Pd8(meso-dpmppm)4(X)2](BF4)2 (X=Cl ( 4 a ), N3 ( 4 b ), CN ( 4 c ), SCN ( 4 d )), were synthesized by using 2 a as a stable good precursor, and characterized by spectroscopic (IR, 1H and 31P NMR, UV-vis-NIR, ESI-MS) measurements and X-ray crystallographic analyses (for 1 , 2 a , b , 3 a , b , e , f , 4 a – d ). On the basis of DFT calculations on the X-ray determined structure of 2 b ( [2b-Pd8]4+ ) and the optimized models [Pd8(meso-Ph2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8Ph8]4+ ) and [Pd8(meso-H2PCH2P(H)CH2P(H)CH2PH2)4(CH3CN)2]4+ ( [Pd8H8]4+ ), with and without empirically calculating dispersion force stabilization energy (B3LYP-D3, B3LYP), the formation energy between the two Pd4 fragments is assumed to involve mainly noncovalent interactions (ca. −70 kcal/mol) with four sets of interligand C−H/π interactions and Pd⋅⋅⋅Pd metallophilic one, while electron shared covalent interactions are almost canceled out within the Pd8 chain. All the compounds isolated are stable in solution and exhibit characteristic absorption at ∼900 nm, which is assignable to a spin allowed HOMO to LUMO transition, and shows temperature dependent intensity change with variable absorption coefficients presumably due to coupling with some thermal vibrations. The structures and electronic states of the Pd8 chains are found finely tunable by varying the terminal capping ligands. In particular, theoretical calculations elucidated that the HOMO-LUMO energy gap is systematically related to the central Pd−Pd distance (2.7319(6)–2.7575(6) Å) by two ways with neutral ligands L ( 1 , 2 , 3 ) and with anionic ligands X ( 4 ), which are reflected on the NIR absorption energy of 867–954 nm. The isocyanide terminated Pd8 complexes ( 3 ) further reacted with excess of RNC (6 eq) to afford the Pd4 complexes, [Pd4(meso-dpmppm)2(RNC)2](BF4)2 ( 13 ), and the cyclic voltammograms of 2 a (L=CH3CN), 3 , and 13 (R=Xyl, Mes, tBu, Cy) demonstrated wide range redox behaviors from 2{Pd4}4+ to 2{Pd4}0 through 2{Pd4}2+↔{Pd8}4+, {Pd8}3+, and {Pd8}2+ strings. The oxidized complexes, [Pd4(meso-dpmppm)2(RNC)3](BF4)4 ( 16 ), were characterized by X-ray analyses, and the two-electron reduced chain of [Pd8(meso-dpmppm)4](BF4)2 ( 7 ) was analyzed by spectroscopic and electrochemical techniques and DFT calculations. Reactions of 2 a with 1 equiv. of aromatic linear bisisocyanide (BI) in CH2Cl2 deposited insoluble coordination polymers, {[Pd8(meso-dpmppm)4(BI)](BF4)4}n ( 5 ), and interestingly, they were soluble in acetonitrile, 31P{1H} and 1H DOSY NMR spectra as well as SAXS curves suggesting that the coordination polymers may exist in acetonitrile as dynamically 1D self-assembled coordination polymers comprising ca. 50 units of the Pd8 rod averaged within the timescale. 相似文献
9.
Kyoichi Hanada Juntaro Nogami Prof. Dr. Kazunori Miyamoto Norihiko Hayase Dr. Yuki Nagashima Yusuke Tanaka Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9313-9319
The enantioselective synthesis of aza[6] and [7]helicene-like molecules have been achieved by the cationic rhodium(I)/axially chiral biaryl bisphosphine complex-catalyzed intramolecular [2+2+2] cycloaddition of cyanodiynes. This protocol was successfully applied to the diastereo- and enantioselective synthesis of an S-shaped double aza[6]helicene-like molecule with a high ee value of 89 %. Although no epimerization and racemization were observed in the double carbo[6]helicene-like molecule at 80 °C, epimerization and racemization of the double aza[6]helicene-like molecule proceeded at 80 °C. This double aza[6]helicene-like molecule showed good fluorescent quantum yields and chiroptical responses under both neutral and acidic conditions. 相似文献
10.