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31.
32.
Tiong PJ Nova A Schwarz AD Selby JD Clot E Mountford P 《Dalton transactions (Cambridge, England : 2003)》2012,41(8):2277-2288
We report a combined experimental and computational comparative study of the reactions of the homologous titanium dialkyl- and diphenylhydrazido and imido compounds Cp*Ti{MeC(N(i)Pr)(2)}(NNR(2)) (R = Me (1) or Ph (2)) and Cp*Ti{MeC(N(i)Pr)(2)}(NTol) (3) with silanes, halosilanes, alkyl halides and [Et(3)NH][BPh(4)]. Compound 1 underwent reversible Si-H 1,2-addition to Ti=N(α) with RSiH(3) (experimental ΔH ca. -17 kcal mol(-1)), and irreversible addition with PhSiH(2)X (X = Cl, Br). DFT found that the reaction products and certain intermediates were stabilised by β-NMe(2) coordination to titanium. The Ti-D bond in Cp*Ti{MeC(N(i)Pr)(2)}(D){N(NMe(2))SiD(2)Ph} underwent σ-bond metathesis with BuSiH(3) and H(2). Compound 1 reacted with RR'SiCl(2) at N(α) to transfer both Cl atoms to Ti; 2 underwent a similar reaction. Compound 3 did not react with RSiH(3) or alkyl halides but formed unstable Ti=N(α) 1,2-addition or N(α) protonation products with PhSiH(2)X or [Et(3)NH][BPh(4)]. Compound 1 underwent exclusive alkylation at N(β) with RCH(2)X (R = H, Me or Ph; X = Br or I) whereas protonation using [Et(3)NH][BPh(4)] occurred at N(α). DFT studies found that in all cases electrophile addition to N(α) (with or without NMe(2) chelation) was thermodynamically favoured compared to addition to N(β). 相似文献
33.
The title compound, rac‐6,13‐dihydro‐6,13‐methanopentacene ( 1 ), has been synthesized and characterized by elemental analysis, FT‐IR, 1H NMR, UV‐Vis, HRMS spectra, cyclic voltammetry and single‐crystal X‐ray diffraction. The crystal belongs to orthorhombic, space group P212121, with Z = 4 and cell dimensions a = 6.0185(4), b = 8.1914(6), c = 31.4080(19) Å. In the crystal structure, two types of intermolecular C–H···π hydrogen bonds are observed, and further stabilize the crystal structure. Its photophysical and electrochemical properties and complementary density functional theory (DFT) calculations are reported. 相似文献
34.
We report here a facile method to immobilize zirconia nanoparticles on a disposable screen‐printed carbon electrode (designated as ZrO2‐SPCE) for phosphate sensor application. Simply by ultrasonicating a bare SPCE in a ZrO2 slurry, ZrO2 nanoparticles can be immobilized effectively on the electrode surface as verified by surface characterization evidences. Using ferricyanide as a redox probe, an increase in the charge transfer resistance (Rct) of ferricyanide upon adsorption of phosphate on ZrO2 is used for the determination of phosphate. This ZrO2‐SPCE phosphate sensor shows a wide linear range up to 1 mM and a detection limit of 1.69 µM (S/N=3). Practical applicability of the ZrO2‐SPCE is demonstrated by detecting phosphate content in human blood samples. 相似文献
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Wolfgang Hnle Walter Schmettow Karl Peters Jen‐Hui Chang Hans Georg von Schnering 《无机化学与普通化学杂志》2004,630(12):1858-1862
The novel ternary polyphosphides M4P21I (M = K, Rb) have been synthesized from the elements in single crystalline form, representing further examples for the formation of mixed crystals between simple salts and binary phosphides. They form as ruby‐red platelets and dark‐red prisms, respectively, and are only slightly sensitive to moisture and oxygen. The compounds are isotypic (Ccmm (no 63); Z = 4; oP104; K4P21I: a = 12.853Å; b = 21.795Å; c = 9.748Å; 1168 hkl, R = 0.033; Rb4P21I: a = 13.281Å; b = 21.868Å; c = 9.771Å; 777 hkl, R = 0.053) and feature corrugated 2D networks formed from two different types of polymerized P7 units. The networks form large cavities filled by M+ and I‐ ions. Zigzag chains of condensed trigonal M6 prisms, centered by the I‐ anions, separate the polyphosphide nets. The mean homoatomic P‐P bond length (d = 2.216Å) corresponds to a P‐P single bond. However, the individual P‐P distances vary with position and function (2.126 ‐ 2.247Å) and these are compared with those of the isolated P21‐3 anion. 相似文献
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The hydrogen molecule ion is a two‐center force system expressed under the prolate spheroidal coordinates, whose quantum motions and quantum trajectories have never been addressed in the literature before. The momentum operators in this coordinate system are derived for the first time from the Hamilton equations of motion and used to construct the Hamiltonian operator. The resulting Hamiltonian comprises a kinetic energy T and a total potential VTotal consisting of the Coulomb potential and a quantum potential. It is shown that the participation of the quantum potential and the accompanied quantum forces in the force interaction within H2+ is essential to develop an electronic motion consistent with the prediction of the probability density function |Ψ|2. The motion of the electron in H2+ can be either described by the Hamilton equations derived from the Hamiltonian H = TK + VTotal or by the Lagrange equations derived from the Lagrangian H = TK ? VTotal. Solving the equations of motion with different initial positions, we show that the solutions yield an assembly of electronic quantum trajectories whose distribution and concentration reconstruct the σ and π molecular orbitals in H2+. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
39.
Harihara Padhy Jen‐Hsien Huang Duryodhan Sahu Dhananjaya Patra Dhananjay Kekuda Chih‐Wei Chu Hong‐Cheu Lin 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4823-4834
A series of soluble donor‐acceptor conjugated polymers comprising of phenothiazine donor and various benzodiazole acceptors (i.e., benzothiadiazole, benzoselenodiazole, and benzoxadiazole) sandwiched between hexyl‐thiophene linkers were designed, synthesized, and used for the fabrication of polymer solar cells (PSC). The effects of the benzodiazole acceptors on the thermal, optical, electrochemical, and photovoltaic properties of these low‐bandgap (LBG) polymers were investigated. These LBG polymers possessed large molecular weight (Mn) in the range of 3.85?5.13 × 104 with high thermal decomposition temperatures, which demonstrated broad absorption in the region of 300?750 nm with optical bandgaps of 1.80?1.93 eV. Both the HOMO energy level (?5.38 to ?5.47 eV) and LUMO energy level (?3.47 to ?3.60 eV) of the LBG polymers were within the desirable range of ideal energy level. Under 100 mW/cm2 of AM 1.5 white‐light illumination, bulk heterojunction PSC devices containing an active layer of electron donor polymers mixed with electron acceptor [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) or [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC71BM) in different weight ratios were investigated. The best performance of the PSC device was obtained by using polymer PP6DHTBT as an electron donor and PC71BM as an acceptor in the weight ratio of 1:4, and a power conversion efficiency value of 1.20%, an open‐circuit voltage (Voc) value of 0.75 V, a short‐circuit current (Jsc) value of 4.60 mA/cm2, and a fill factor (FF) value of 35.0% were achieved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
40.
Jen‐Taut Yeh Chi‐Hui Tsou Wei Lu Ya‐Ming Li Han Wen Xiao Chi‐Yuan Huang Kan‐Nan Chen Chin‐San Wu Wan‐Lan Chai 《Journal of Polymer Science.Polymer Physics》2010,48(9):913-920
Fourier transform infrared and nuclear magnetic resonance results suggest that the carboxylic acid groups of poly(lactic acid) (PLA) molecules react with the hydroxyl groups of FePol (FP) molecules during the melt‐blending of PLAxFPy specimens. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) experiments of PLA and PLA/FP specimens suggest that only small amounts of poor PLA and/or FP crystals are present in their corresponding melt crystallized specimens. In fact, the percentage crystallinity, peak melting temperature, and onset re‐crystallization temperature values of PLA/FP specimens reduce gradually as their FP contents increase. However, the glass transition temperatures of PLA molecules found by DSC and DMA reduce to a minimum value as the FP contents of PLAxFPy specimens reach 6 wt %. Further DMA and morphological analysis of PLA/FP specimens reveal that FP molecules are compatible with PLA molecules at FP contents equal to or less than 6 wt %, as no distinguished phase‐separated FP droplets and tan δ transitions were found on fracture surfaces and tan δ curves of PLA/FP specimens, respectively. In contrast to PLA, the FP specimen exhibits highly deformable and tearing properties. After blending proper amounts of FP in PLA, the inherent brittle deformation and poor tearing behavior of PLA were successfully improved. Possible reasons accounting for these interesting crystallization, compatible and tearing properties of PLA/FP specimens are proposed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 913–920, 2010 相似文献