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Jianhuai Ye Dr. Sayaka Hatano Prof. Dr. Manabu Abe Prof. Dr. Ryohei Kishi Yusuke Murata Prof. Dr. Masayoshi Nakano Prof. Dr. Waldemar Adam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(7):2299-2306
In the photochemical denitrogenation of 1,4‐diaryl‐2,3‐diazabicyclo[2.2.1]heptane ( AZ6 ) bearing sterically hindered substituents, a curious new absorption band at about 450 nm was observed under low‐temperature matrix conditions, together with the previously well‐characterized planar singlet diradical pl‐1 DR6 with λmax=≈580 nm. The 450 nm species was electron paramagnetic resonance (EPR)‐silent. Instead of generating the planar diradical pl‐1 DR6 and the precursor azoalkane AZ6 upon warming, the ring‐closed bicyclo[2.1.0]pentane derivative SB6 , that is, the AZ6 denitrogenation product was identified. Based on product analysis, low‐temperature spectroscopic observations, high‐level quantum‐mechanical computations, viscosity effect, and laser‐flash photolysis, the puckered singlet diradicaloid puc‐1 DR6 was assigned to the new 450 nm absorption. The latter was detected experimentally at the same time as the planar singlet diradical pl‐1 DR6 . Sterically demanding substituents as well as viscosity impediments were essential for the detection of the experimentally hitherto unknown puckered singlet cyclopentane‐1,3‐diyl diradicaloid puc‐1 DR6 , that is, the third isomer in homolysis. The present findings should stimulate future work on the mechanistically fascinating stereoselectivity documented in the formation of bicyclo[2.1.0]pentanes during the 2,3‐diazabicyclo[2.2.1]heptane denitrogenation. 相似文献
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Noa Lachman Yifat Harel Adam Green Noa Iuster Jean‐Paul Lellouche H. Daniel Wagner 《Journal of Polymer Science.Polymer Physics》2012,50(14):957-962
In this article, Multi‐Walled Carbon Nanotubes (MWCNTs) of varying diameters, both untreated and polycarboxylated, were dispersed at constant weight percentage in an epoxy matrix, and resulting fracture toughnesses (KIc) were measured in each case. We show that changing the MWCNT diameter has two effects on the composite fracture toughness: (i) a small MWCNT diameter enables larger interfacial surface for adhesion maximization, which increases toughness; (ii) at the same time, it limits the available pull‐out energy and reduces the MWCNT ability to homogeneously disperse in the matrix due to this same large active surface: this decreases toughness. Most commercially available MWCNTs have a length range of several μm, thus an optimal diameter exists which depends on MWCNT wall thickness and surface treatment. Such optimal diameter maximizes pull‐out energy and thus composite fracture toughness. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
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Dr. Adam A. Sobczuk Dr. Youichi Tsuchiya Dr. Tomohiro Shiraki Dr. Shun‐ichi Tamaru Prof. Seiji Shinkai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(10):2832-2838
A unique class of oligothiophene‐based organogelator bearing two crown ethers at both ends was synthesized. This compound could gelatinize several organic solvents, forming one‐dimensional fibrous aggregates. From the observation of circular dichroism, it was confirmed that the helical handedness of the fibrous assembly is controllable by the chirality of 1,2bisammonium guests, thus suggesting that one guest molecule bridges two gelator molecules through the crown–ammonium interaction. Interestingly, we have found that such chirality is created by thermal gelation, whereas it disappears by thixotropic gelation. The new finding implies that the present organogel system is applicable as a reversible switching memory device, featuring memory creation by a heat mode and memory erasing by a mechanical mode. 相似文献
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Eric R. Beckel Neil B. Cramer Adam W. Harant Christopher N. Bowman Corresponding author 《Liquid crystals》2013,40(11):1343-1350
Electro-optic properties of polymer stabilized ferroelectric liquid crystal (PSFLC) systems are examined as a function of varying concentrations of either a linear or crosslinked thiol-ene polymer. The thiol-ene method of polymer stabilization is a drastic change from previous studies designed to avert the problem of polymer phase separation. FLC rise time and tilt angle measurements were used to determine the effects of the polymer network on the optical properties of the system. The addition of monomer impurities to both systems demonstrated a reduction in tilt angle, which translated into decreased switching speeds in both systems prior to polymerization. The crosslinked thiol-ene system showed increased switching times due to the creation of polymer in the interlayer spacing of the FLC, but exhibited minimal increase in the rotational viscosity of the system. In addition, the crosslinked polymer systems resulted in an increase in the liquid crystalline order, which produced an increase in the contrast ratio of the system. The linear polymer system showed drastically different results as compared with the crosslinked system. The rise time and tilt angle measurements decreased upon polymerization of the linear thiol-ene and the rotational viscosity and contrast ratio values also decreased. We suggest that the linear thiol-ene polymer phase separation from the interlayer spacing leads to a microscopic misalignment of the FLC molecules, causing a decrease in the optical properties of the LC. 相似文献
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Catalytic activity of nickel(II), copper(II) and oxovanadium(II)‐dihydroindolone complexes towards homogeneous oxidation reactions
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Mohamed Shaker S. Adam 《应用有机金属化学》2018,32(4)
Three novel paramagnetic metal complexes (MH2ID) of Ni2+, Cu2+ and VO2+ ions with 3‐hydroxy‐3,3’‐biindoline‐2,2’‐dione (dihydroindolone, H4ID) were synthesized and characterized by different spectroscopic methods. The ligand (H4ID) was synthesized via homocoupling reaction of isatin in presence of phenylalanine in methanol. Complexation of low valent Ni2+, Cu2+ ions and high valent VO2+ ions with H4ID carried out in 1: 2 molar ratios. A comparison in the catalytic potential of paramagnetic complexes of low and high valent metal ion was explored in the oxidation processes of cis‐cyclooctene, benzyl alcohol and thiophene by an aqueous H2O2, as a green terminal oxidant, in the presence and absence of acetonitrile, as an organic solvent, at 85 °C. NiH2ID, CuH2ID and VOH2ID show good catalytic activity, i.e. good chemo‐ and regioselectivity. VOH2ID has the highest catalytic potential compared to both Ni2+‐ and Cu2+‐species in the same homogenous aerobic atmosphere. Catalytic oxidation of other alkenes and alcohols was also studied using NiH2ID, CuH2ID or VOH2ID as a pre‐catalyst by an aqueous H2O2. A mechanistic pathway for those oxidation processes was proposed. 相似文献
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