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11.
Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks 下载免费PDF全文
Prof. Hongzhi Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4731-4738
Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission. 相似文献
12.
Mitsuki Yamashita Yuna Kawasumi Yuki Tachibana Dr. Shinnosuke Horiuchi Dr. Koji Yamamoto Prof. Tetsuro Murahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1212-1216
Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd4]4+ chain. 相似文献
13.
《Tetrahedron letters》2019,60(24):1582-1586
Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred. 相似文献
14.
The preliminary results of the hydroformylation of 2-phenylsulfonyl substituted norbornene and norbornadiene derivatives catalyzed by the unmodified Rh(CO)2acac system are presented. The reaction, occurring under standard oxo conditions, gives polyfunctionalized exo norbornene- and exo norbornanecarboxaldehydes. The effect of the phenylsulfonyl group has been evaluated: it has been found that the steric properties of the sulfonyl substituent, more than the electronic ones, influence the regioselectivity of the process. 相似文献
15.
采用基于第一原理的全势能线性缀加平面波加局域轨道((L)APW lo)方法对Nd(Fe,Si)11Cx化合物(x=0,2)的电子结构进行了计算,得到了化合物态密度和磁矩等信息.计算结果表明NdFe9Si2化合物中Si原子主要与4b和32i位Fe原子产生杂化,导致Fe原子磁矩减小.NdFe9Si2C2化合物C原子使32i位Fe原子磁矩进一步降低,同时减弱了Si原子的影响,使得4b位Fe原子磁矩增大. 相似文献
16.
S. Meenakshi B.K. Godwal I. Orgzall S. Tkachev 《Journal of Physics and Chemistry of Solids》2006,67(8):1660-1667
We report the results of an X-ray diffraction study of CdAl2Se4 and of Raman studies of HgAl2Se4 and ZnAl2Se4 at room temperature, and of CdAl2S4 and CdAl2Se4 at 80 K at high pressure. The ambient pressure phase of CdAl2Se4 is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl2Se4 and ZnAl2Se4 reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl2S4 and CdAl2Se4, which shows a very weak temperature dependence of the Raman-active phonon modes. 相似文献
17.
Electrical impedance measurements of Na3H(SO4)2 were performed as a function of both temperature and frequency. The electrical conductivity and dielectric relaxation have been evaluated. The temperature dependence of electrical conductivity reveals that the sample crystals transformed to the fast ionic state in the high temperature phase. The dynamical disordering of hydrogen and sodium atoms and the orientation of SO4 tetrahedra results in fast ionic conductivity. In addition to the proton conduction, the possibility of a Na+ contribution to the conductivity in the high temperature phase is proposed. The frequency dependence of AC conductivity is proportional to ωs. The value of the exponent, s, lies between 0.85 and 0.46 in the room temperature phase, whereas it remains almost constant, 0.6, in the high-temperature phase. The dielectric dispersion is examined using the modulus formalism. An Arrhenius-type behavior is observed when the crystal undergoes the structural phase transition. 相似文献
18.
R.S. Gonnelli A. CalzolariD. Daghero G.A. UmmarinoV.A. Stepanov P. FinoG. Giunchi S. CeresaraG. Ripamonti 《Journal of Physics and Chemistry of Solids》2002,63(12):2319-2323
We studied the voltage and temperature dependency of the dynamic conductance of normal metal-MgB2 junctions obtained either with the point-contact technique (with Au and Pt tips) or by making Ag-paint spots on the surface of MgB2 samples. The fit of the conductance curves with the generalized BTK model gives evidence of pure s-wave gap symmetry. The temperature dependency of the gap, measured in Ag-paint junctions (dirty limit), follows the standard BCS curve with 2Δ/kBTc=3.3. In out-of-plane, high-pressure point-contacts we obtained almost ideal Andreev reflection characteristics showing a single small s-wave gap Δ=2.6±0.2 meV (clean limit). 相似文献
19.
Chemical bonding in isolated molecules and crystals of zwitterionic pentacoordinate silicon chelates
The electronic structures of a number of zwitterionic pentacoordinate silicon chelates were investigated using the results of X-ray diffraction studies and quantum-chemical calculatoins by the MPW1PW91/6-311G(d) method. The topological analysis of the electron density distribution function and the study in the framework of the natural bond orbital partitioning scheme showed that the character of chemical bonding in the axial fragments of the molecules under consideration changes from dative to three-center, four-electron as the silicon atom assumes a trigonal-bipyramidal coordination. 相似文献
20.
Jong Chan Lee Jin Young Park So Young Yoon Yong Hun Bae Seung Jun Lee 《Tetrahedron letters》2004,45(1):191-193
A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described. 相似文献