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971.
Photo-reactive bisazide in a polymer matrix containing acryloyl groups on the side chain was investigated as a photoalignment layer for polymerizable liquid crystals (PLC). We found the thin film of bisazide (2,6-bis(4-azidobenzylidene)-4-methyl-1-cyclohexanone) in a polymer matrix, irradiated by linearly polarised ultraviolet light (LPUVL), was able to homogeneously align PLC. The LPUVL irradiation dose changed the orientation direction of the PLC on the thin film of bisazide in the polymer matrix. In addition, the direction of the slow axis for the retardation of the photoalignment layer changed from parallel to perpendicular to the LPUVL electric field with the irradiation dose. From these results, it was suggested that the PLC was likely to be aligned along the slow axis of the retardation of the photoalignment layer. We concluded that the key mechanism that changed the direction of the slow axis in a plane was the photoreaction of azide–acrylate at low irradiation dose and that of bis(benzylidene)cyclohexanone at high irradiation dose. Although the photoalignment as a result of a simple photo cross-linking was previously little known except for photo-dimerisation, we revealed that the photoaddition of azide–acrylate is able to achieve the photoalignment. 相似文献
972.
A series of C-7 modified analogues of casuarine have been synthesized from sugar-derived nitrone and assayed against various glycosidases. Introduction of C-7 aminomethyl or amide group led to sharp decrease of the inhibitory activities. 相似文献
973.
Synthetic Control of the Excited‐State Dynamics and Circularly Polarized Luminescence of Fluorescent “Push–Pull” Tetrathia[9]helicenes 下载免费PDF全文
Yuki Yamamoto Dr. Hayato Sakai Dr. Junpei Yuasa Prof. Yasuyuki Araki Prof. Takehiko Wada Prof. Tomo Sakanoue Prof. Taishi Takenobu Prof. Tsuyoshi Kawai Prof. Taku Hasobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):4263-4273
A series of fluorescent “push‐pull” tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited‐state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the “push–pull” character, which was enhanced by further introduction of an electron‐releasing Me2N group or an electron‐withdrawing NC group onto the quinoxaline unit (denoted as Me2N‐QTTH and NC‐QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (ΦFL) were achieved. In particular, the maximum ΦFL of Me2N‐QTTH was 0.43 in benzene (NC‐QTTH: ΦFL=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; ΦFL=0.02). These enhancements were also explained by kinetic discussion of the excited‐state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the ΦFL values thus enabled us to show the excellent CPL properties. The value of anisotropy factor gCPL (normalized difference in emission of right‐handed and left‐handed circularly polarized light) was estimated to be 3.0×10?3 for NC‐QTTH. 相似文献
974.
975.
Nozomi Terada Keisuke Uematsu Ryota Higuchi Dr. Yuki Tokimaru Yosuke Sato Dr. Koji Nakano Prof. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(36):9342-9349
A double helicene with a spiro-Si linker ( 4 ) was synthesized by four successive nucleophilic substitutions on SiCl4. Its (P,P), (M,M) and (P,M) isomers were isolated and characterized by single crystal X-ray analysis. Due to the central spirosilabi[fluorene] moiety, the two helicene units in 4 are symmetrically and nearly perpendicularly arranged. (P,P)- 4 and (M,M)- 4 exhibit unique optical properties attributable to the LUMO spiro-conjugation between the two sila[7]helicene units. 相似文献
976.
Journal of Theoretical Probability - We investigate a Belinschi–Nica-type semigroup for free and Boolean max-convolutions. We prove that this semigroup at time one connects limit theorems for... 相似文献
977.
Structure and dynamics of room temperature ionic liquids with bromide anion: results from 81Br NMR spectroscopy 下载免费PDF全文
Takatsugu Endo Mamoru Imanari Yuki Hidaka Hiroko Seki Keiko Nishikawa Sabyasachi Sen 《Magnetic resonance in chemistry : MRC》2015,53(5):369-378
We report the results of a comprehensive 81Br NMR spectroscopic study of the structure and dynamics of two room temperature ionic liquids (RTILs), 1‐butyl‐3‐methylimidazolium bromide ([C4mim]Br) and 1‐butyl‐2,3‐dimethylimidazolium bromide ([C4C1mim]Br), in both liquid and crystalline states. NMR parameters in the gas phase are also simulated for stable ion pairs using quantum chemical calculations. The combination of 81Br spin‐lattice and spin‐spin relaxation measurements in the motionally narrowed region of the stable liquid state provides information on the correlation time of the translational motion of the cation. 81Br quadrupolar coupling constants (CQ) of the two RTILs were estimated to be 6.22 and 6.52 MHz in the crystalline state which were reduced by nearly 50% in the liquid state, although in the gas phase, the values are higher and span the range of 7–53 MHz depending on ion pair structure. The CQ can be correlated with the distance between the cation–anion pairs in all the three states. The 81Br CQ values of the bromide anion in the liquid state indicate the presence of some structural order in these RTILs, the degree of which decreases with increasing temperature. On the other hand, the ionicity of these RTILs is estimated from the combined knowledge of the isotropic chemical shift and the appropriate mean energy of the excited state. [C4C1mim]Br has higher ionicity than [C4mim]Br in the gas phase, while the situation is reverse for the liquid and the crystalline states. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
978.
Cover Picture: Electrochemically Mediated Atom Transfer Radical Polymerization from a Substrate Surface Manipulated by Bipolar Electrolysis: Fabrication of Gradient and Patterned Polymer Brushes (Angew. Chem. Int. Ed. 13/2015) 下载免费PDF全文
979.
Dr. Roman Savka M. Sc. Marvin Bergmann Yuki Kanai Sabine Foro Prof. Dr. Herbert Plenio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9667-9675
Based on 1‐amino‐4‐hydroxy‐triptycene, new saturated and unsaturated triptycene‐NHC (N‐heterocyclic carbene) ligands were synthesized from glyoxal‐derived diimines. The respective carbenes were converted into metal complexes [(NHC)MX] (M=Cu, Ag, Au; X=Cl, Br) and [(NHC)MCl(cod)] (M=Rh, Ir; cod=1,5‐cyclooctadiene) in good yields. The new azolium salts and metal complexes suffer from limited solubility in common organic solvents. Consequently, the introduction of solubilizing groups (such as 2‐ethylhexyl or 1‐hexyl by O‐alkylation) is essential to render the complexes soluble. The triptycene unit infers special steric properties onto the metal complexes that enable the steric shielding of selected areas close to the metal center. Next, chiral and meso‐triptycene based N‐heterocyclic carbene ligands were prepared. The key step in the synthesis of the chiral ligand is the Buchwald–Hartwig amination of 1‐bromo‐4‐butoxy‐triptycene with (1S,2S)‐1,2‐diphenyl‐1,2‐diaminoethane, followed by cyclization to the azolinium salt with HC(OEt)3. The analogous reaction with meso‐1,2‐diphenyl‐1,2‐diaminoethane provides the respective meso‐azolinium salt. Both the chiral and meso‐azolinium salts were converted into metal complexes including [(NHC)AuCl], [(NHC)RhCl(cod)], [(NHC)IrCl(cod)], and [(NHC)PdCl(allyl)]. An in situ prepared chiral copper complex was tested in the enantioselective borylation of α,β‐unsaturated esters and found to give an excellent enantiomeric ratio (er close to 90:10). 相似文献
980.