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91.
Reductive Coupling of Diynes at Rhodium Gives Fluorescent Rhodacyclopentadienes or Phosphorescent Rhodium 2,2’‐Biphenyl Complexes 下载免费PDF全文
Carolin Sieck Dr. Meng Guan Tay Dr. Marie‐Hélène Thibault Dr. Robert M. Edkins Dr. Karine Costuas Prof. Dr. Jean‐François Halet Dr. Andrei S. Batsanov Dr. Martin Haehnel Dr. Katharina Edkins Dr. Andreas Lorbach Dr. Andreas Steffen Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10523-10532
Reactions of [Rh(κ2‐O,O‐acac)(PMe3)2] (acac=acetylacetonato) and α,ω‐bis(arylbutadiynyl)alkanes afford two isomeric types of MC4 metallacycles with very different photophysical properties. As a result of a [2+2] reductive coupling at Rh, 2,5‐bis(arylethynyl)rhodacyclopentadienes ( A ) are formed, which display intense fluorescence (Φ=0.07–0.54, τ=0.2–2.5 ns) despite the presence of the heavy metal atom. Rhodium biphenyl complexes ( B ), which show exceptionally long‐lived (hundreds of μs) phosphorescence (Φ=0.01–0.33) at room temperature in solution, have been isolated as a second isomer originating from an unusual [4+2] cycloaddition reaction and a subsequent β‐H‐shift. We attribute the different photophysical properties of isomers A and B to a higher excited state density and a less stabilized T1 state in the biphenyl complexes B , allowing for more efficient intersystem crossing S1→Tn and T1→S0. Control of the isomer distribution is achieved by modification of the bis‐ (diyne) linker length, providing a fundamentally new route to access photoactive metal biphenyl compounds. 相似文献
92.
Philipp R. Matthes Jörn Nitsch Ana Kuzmanoski Prof. Claus Feldmann Dr. Andreas Steffen Prof. Todd B. Marder Prof. Klaus Müller‐Buschbaum 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17369-17378
A series of 12 dinuclear complexes [Ln2Cl6(μ‐4,4′‐bipy)(py)6], Ln=Y, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, ( 1 – 12 , respectively) was synthesized by an anhydrous solvothermal reaction in pyridine. The complexes contain a 4,4′‐bipyridine bridge and exhibit a coordination sphere closely related to luminescent lanthanide MOFs based on LnCl3 and 4,4‐bipyridine. The dinuclear complexes therefore function as a molecular model system to provide a better understanding of the luminescence mechanisms in the Ln‐N‐MOFs ${\hbox{}{{\hfill 2\atop \hfill \infty }}}$ [Ln2Cl6(4,4′‐bipy)3] ? 2(4,4′‐bipy). Accordingly, the luminescence properties of the complexes with Ln=Y, Sm, Eu, Gd, Tb, Dy, ( 1 , 4 – 8 ) were determined, showing an antenna effect through a ligand–metal energy transfer. The highest efficiency of luminescence is observed for the terbium‐based compound 7 displaying a high quantum yield (QY of 86 %). Excitation with UV light reveals typical emission colors of lanthanide‐dependent intra 4f–4f‐transition emissions in the visible range (TbIII: green, EuIII: red, SmIII: salmon red, DyIII: yellow). For the GdIII‐ and YIII‐containing compounds 6 and 1 , blue emission based on triplet phosphorescence is observed. Furthermore, ligand‐to‐metal charge‐transfer (LMCT) states, based on the interaction of Cl? with EuIII, were observed for the EuIII compound 5 including energy‐transfer processes to the EuIII ion. Altogether, the model complexes give further insights into the luminescence of the related MOFs, for example, rationalization of Ln‐independent quantum yields in the related MOFs. 相似文献
93.
William Clegg Fiona J. Lawlor Gerry Lesley Todd B. Marder Nicholas C. Norman A.Guy Orpen Michael J. Quayle Craig R. Rice Andrew J. Scott Fabio E.S. Souza 《Journal of organometallic chemistry》1998,550(1-2)
The synthesis and spectroscopic characterisation of the new diborane(4) compounds B2(1,2-O2C6Cl4)2 and B2(1,2-O2C6Br4)2 are reported together with the diborane(4) bis-amine adduct [B2(calix)(NHMe2)2] (calix=Butcalix[4]arene). B–B bond oxidative addition reactions between the platinum(0) compound [Pt(PPh3)2(η-C2H4)] and the diborane(4) compounds B2(1,2-S2C6H4)2, B2(1,2-O2C6Cl4)2 and B2(1,2-O2C6Br4)2 are also described which result in the platinum(II) bis-boryl complexes cis-[Pt(PPh3)2{B(1,2-S2C6H4)}2], cis-[Pt(PPh3)2{B(1,2-O2C6Cl4)}2] and cis-[Pt(PPh3)2{B(1,2-O2C6Br4)}2] respectively, the former two having been characterised by X-ray crystallography. In addition, the platinum complex [Pt(PPh3)2(η-C2H4)] reacts with XB(1,2-O2C6H4) (X=Cl, Br) affording the mono-boryl complexes trans-[PtX(PPh3)2{B(1,2-O2C6H4)}] as a result of oxidative addition of the B–X bonds to the Pt(0) centre; the chloro derivative has been characterised by X-ray crystallography. 相似文献
94.
Marder B.M. Clark M.C. Bacon L.D. Hoffman J.M. Lemke R.W. Coleman P.D. 《IEEE transactions on plasma science. IEEE Nuclear and Plasma Sciences Society》1992,20(3):312-331
A compact device, called a split-cavity oscillator, whose self-excited oscillating electromagnetic field converts a large-area steady electron beam into one that is highly density modulated, is described. It does this in a short beam travel length, easing both space-charge and pinching limitations. Thus, high currents are possible without requiring a magnetic guide field. Methods for converting the modulated output beam into high-power microwaves are discussed, as are ways to phase-lock several oscillators together. Analytic theory, numerical simulations, and experiments describing the device are presented 相似文献
95.
Shoaee S Eng MP An Z Zhang X Barlow S Marder SR Durrant JR 《Chemical communications (Cambridge, England)》2008,(40):4915-4917
We report on photoinduced charge separation in solid films of two perylene diimides; intramolecular charge separation and recombination is correlated with a reduction in the yield of long-lived, intermolecular charge-separated species. 相似文献
96.
Jan Maier Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(30):7978-7991
With the rapid development of the hexadehydro-Diels-Alder reaction (HDDA) from its first discovery in 1997, the question of whether a concerted or stepwise mechanism better describes the thermally activated formation of ortho-benzyne from a diyne and a diynophile has been debated. Mechanistic and kinetic investigations were able to show that this is not a black or white situation, as minor changes can tip the balance. For that reason, especially, linked yne-diynes were studied to examine steric, electronic, and radical-stabilizing effects of their terminal substituents on the reaction mechanism and kinetics. Furthermore, the influence of the nature of the linker on the HDDA reaction was explored. The more recently discovered photochemical HDDA reaction also gives ortho-arynes, which display the same reactivity as the thermally generated ones, but their formation might not proceed by the same mechanism. This minireview summarizes the current state of mechanistic understanding of the HDDA reaction. 相似文献
97.
Cho JY Barlow S Marder SR Fu J Padilha LA Van Stryland EW Hagan DJ Bishop M 《Optics letters》2007,32(6):671-673
The two-photon absorption spectrum of a nickel bis(dithiolene) complex with extended conjugation and pi-donor substitution is measured by using Z-scan and pump-probe techniques with femtosecond pulses over the spectral range from 1.20 to 1.58 microm, which includes much of the telecommunications range. The peak two-photon cross section of over 5000 GM (1 GM = 10(-50) cm4 s photon(-1) molecule(-1)) occurs at approximately 1.24 microm, with significant two-photon absorption (>440 GM) throughout the spectral range examined. 相似文献
98.
99.
Room Temperature Ring Expansion of N‐Heterocyclic Carbenes and BB Bond Cleavage of Diboron(4) Compounds 下载免费PDF全文
Sabrina Pietsch Ursula Paul Dr. Ian A. Cade Dr. Michael J. Ingleson Prof. Dr. Udo Radius Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(25):9018-9021
We report the isolation and detailed structural characterization, by solid‐state and solution NMR spectroscopy, of the neutral mono‐ and bis‐NHC adducts of bis(catecholato)diboron (B2cat2). The bis‐NHC adduct undergoes thermally induced rearrangement, forming a six‐membered ‐B?C?N?C?C‐N‐heterocyclic ring via C?N bond cleavage and ring expansion of the NHC, whereas the mono‐NHC adduct is stable. Bis(neopentylglycolato)diboron (B2neop2) is much more reactive than B2cat2 giving a ring expanded product at room temperature, demonstrating that ring expansion of NHCs can be a very facile process with significant implications for their use in catalysis. 相似文献
100.
Mirjam J. Krahfuß Dr. Jörn Nitsch Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Todd B. Marder Prof. Dr. Udo Radius 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(49):11276-11292
A study on the reactivity of the N-heterocyclic silylene Dipp2NHSi (1,3-bis(diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-yliden) with the transition metal complexes [Ni(CO)4], [M(CO)6] (M=Cr, Mo, W), [Mn(CO)5(Br)] and [(η5-C5H5)Fe(CO)2(I)] is reported. We demonstrate that N-heterocyclic silylenes, the higher homologues of the now ubiquitous NHC ligands, show a remarkably different behavior in coordination chemistry compared to NHC ligands. Calculations on the electronic features of these ligands revealed significant differences in the frontier orbital region which lead to some peculiarities of the coordination chemistry of silylenes, as demonstrated by the synthesis of the dinuclear, NHSi-bridged complex [{Ni(CO)2(μ-Dipp2NHSi)}2] ( 2 ), complexes [M(CO)5(Dipp2NHSi)] (M=Cr 3 , Mo 4 , W 5 ), [Mn(CO)3(Dipp2NHSi)2(Br)] ( 9 ) and [(η5-C5H5)Fe(CO)2(Dipp2NHSi-I)] ( 10 ). DFT calculations on several model systems [Ni(L)], [Ni(CO)3(L)], and [W(CO)5(L)] (L=NHC, NHSi) reveal that carbenes are typically the much better donor ligands with a larger intrinsic strength of the metal–ligand bond. The decrease going from the carbene to the silylene ligand is mainly caused by favorable electrostatic contributions for the NHC ligand to the total bond strength, whereas the orbital interactions were often found to be higher for the silylene complexes. Furthermore, we have demonstrated that the contribution of σ- and π-interaction depends significantly on the system under investigation. The σ-interaction is often much weaker for the NHSi ligand compared to NHC but, interestingly, the π-interaction prevails for many NHSi complexes. For the carbonyl complexes, the NHSi ligand is the better σ-donor ligand, and contributions of π-symmetry play only a minor role for the NHC and NHSi co-ligands. 相似文献