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101.
Prof. Takanori Suzuki Yuto Sakano Dr. Tomohiro Iwai Dr. Shinichi Iwashita Dr. Youhei Miura Dr. Ryo Katoono Prof. Hidetoshi Kawai Prof. Kenshu Fujiwara Prof. Yasushi Tsuji Prof. Takanori Fukushima 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):117-123
When two benzene rings are fused to a tetraaryl‐o‐quinodimethane skeleton, sterically hindered helical molecules 1 acquire a high thermodynamic stability. Because the tetraarylbutadiene subunit contains electron‐donating alkoxy groups, 1 undergo reversible two‐electron oxidation to 2 2+, which can be isolated as deeply colored stable salts. Intramolecular transfer of the point chirality (e.g., sec‐butyl) on the aryl groups to helicity induces a diastereomeric preference in dications 2 b 2+ and 2 c 2+, which represents an efficient method for enhancing circular‐dichroism signals. Thus, those redox pairs can serve as new electrochiroptical response systems. X‐ray analysis of dication 2 2+ revealed π–π stacking interaction of the diarylmethylium moieties, which is also present in solution. The stacking geometry is the key contributor to the chirosolvatochromic response. 相似文献
102.
Synthesis,Crystal Packing,and Ambipolar Carrier Transport Property of Twisted Dibenzo[g,p]chrysenes 下载免费PDF全文
Dr. Yasuyuki Ueda Dr. Hayato Tsuji Dr. Hideyuki Tanaka Prof. Dr. Eiichi Nakamura 《化学:亚洲杂志》2014,9(6):1623-1628
A versatile method for the synthesis of dibenzo[g,p]chrysene (DBC) derivatives based on regio‐ and stereoselective stannyllithiation to diarylacetylenes is described. This method affords a variety of DBCs possessing both electron‐donating and electron‐withdrawing functional groups. These twisted molecules take brickwork packing structures in single crystals. Thus, ambipolar carrier transport properties with mobility values of up to 10?3 cm2 V?1 s?1 in the amorphous state were achieved. Functional groups on DBC frameworks are considered to increase carrier mobility through the enhancement of intermolecular interactions in the brickwork packing structures. 相似文献
103.
Facile Insertion of Carbon Dioxide into Cu2(μ‐H) Dinuclear Units Supported by Tetraphosphine Ligands 下载免费PDF全文
Kanako Nakamae Dr. Bunsho Kure Prof. Takayuki Nakajima Prof. Yasuyuki Ura Prof. Tomoaki Tanase 《化学:亚洲杂志》2014,9(11):3106-3110
Reactions of meso‐bis[(diphenylphosphinomethyl)phenylphosphino]methane (dpmppm) with CuI species in the presence of NaBH4 afforded di‐ and tetranuclear copper hydride complexes, [Cu2(μ‐H)(μ‐dpmppm)2]X ( 1 ) and [Cu4(μ‐H)2(μ4‐H)(μ‐dpmppm)2]X ( 2 ) (X=BF4, PF6). Complex 1 undergoes facile insertion of CO2 (1 atm) at room temperature, leading to a formate‐bridged dicopper complex [Cu2(μ‐HCOO)(dpmppm)2]X ( 3 ). The experimental and DFT theoretical studies clearly demonstrate that CO2 insertion into the Cu2(μ‐H) unit occurred with the flexible dicopper platform. Complex 2 also undergoes CO2 insertion to give a formate‐bridged complex, [Cu4(μ‐HCOO)3(dpmppm)2]X, during which the square Cu4 framework opened up to a linear tetranuclear chain. 相似文献
104.
105.
Jinhua Hong Shunsuke Kobayashi Akihide Kuwabara Yumi H. Ikuhara Yasuyuki Fujiwara Yuichi Ikuhara 《Molecules (Basel, Switzerland)》2021,26(12)
Solid electrolytes, such as perovskite Li3xLa2/1−xTiO3, LixLa(1−x)/3NbO3 and garnet Li7La3Zr2O12 ceramic oxides, have attracted extensive attention in lithium-ion battery research due to their good chemical stability and the improvability of their ionic conductivity with great potential in solid electrolyte battery applications. These solid oxides eliminate safety issues and cycling instability, which are common challenges in the current commercial lithium-ion batteries based on organic liquid electrolytes. However, in practical applications, structural disorders such as point defects and grain boundaries play a dominating role in the ionic transport of these solid electrolytes, where defect engineering to tailor or improve the ionic conductive property is still seldom reported. Here, we demonstrate a defect engineering approach to alter the ionic conductive channels in LixLa(1−x)/3NbO3 (x = 0.1~0.13) electrolytes based on the rearrangements of La sites through a quenching process. The changes in the occupancy and interstitial defects of La ions lead to anisotropic modulation of ionic conductivity with the increase in quenching temperatures. Our trial in this work on the defect engineering of quenched electrolytes will offer opportunities to optimize ionic conductivity and benefit the solid electrolyte battery applications. 相似文献
106.
We study the far-field characteristics of oval-resonator laser diodes made of an GaAs/Al(x)Ga(1-x)As quantum well. The resonator shapes are various oval geometries, thereby probing chaotic and mixed classical dynamics. The far-field pattern shows a pronounced fine structure that strongly depends on the cavity shape. Comparing the experimental data with ray-model simulations for a Fresnel billiard yields convincing agreement for all geometries and reveals the importance of the underlying classical phase space for the lasing characteristics. 相似文献
107.
We obtained high-quality lowest-loss-mode lasing in quasi-stadium laser diodes having unstable resonators that consisted of two curved end mirrors and two straight sidewall mirrors. The laser diodes were fabricated by applying a reactive ion etching technique to a metal-organic chemical-vapor deposition-grown graded-index separate-confinement heterostructure single-quantum-well GaAs/AlGaAs structure. The electrode contact area of the laser diodes was formed along unstable periodic orbits, along which the optical beams are localized. Highly directional fan-out beams corresponding to the numerically obtained lowest loss mode were emitted from the end mirrors under CW operation at room temperature. 相似文献
108.
Fukushima Yasumasa Aikawa Shunichi 《Journal of inclusion phenomena and macrocyclic chemistry》2021,100(1-2):143-148
Journal of Inclusion Phenomena and Macrocyclic Chemistry - A colorimetric chemosensor is reported for Cu2+ by a simple mixture of two commercially available reagents, ponceau 6R (P6R) and... 相似文献
109.
Formation of One‐Dimensional Helical Columns and Excimerlike Excited States by Racemic Quinoxaline‐Fused [7]Carbohelicenes in the Crystal 下载免费PDF全文
Dr. Hayato Sakai Sho Shinto Prof. Yasuyuki Araki Prof. Takehiko Wada Prof. Tomo Sakanoue Prof. Taishi Takenobu Prof. Taku Hasobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10099-10109
A series of quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light‐emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited‐state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady‐state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single‐crystal analysis. Introduction of appropriate substituents (i.e., 4‐methoxyphenyl) in the HeQu unit enabled the construction of one‐dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π‐stacking between two neighboring [7]carbohelicenes and intercolumn CH ??? N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time‐resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units. 相似文献
110.
Dr. Hiromu Kashida Hidenori Azuma Ryoko Maruyama Dr. Yasuyuki Araki Prof. Dr. Takehiko Wada Prof. Dr. Hiroyuki Asanuma 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11456-11459
Herein we report the construction of efficient light-harvesting antennae by hybridization of DNA oligonucleotides containing high densities of fluorophores into DNA junctions through d -threoninol. Six pyrene donors could be incorporated into each arm without self-quenching. A perylene acceptor was located at the center of the junction. Antenna effects of a duplex and three- to eight-way junctions were systematically compared. Six- and eight-way junctions had the highest antenna effects, and their effective absorption coefficients were 8.5 times higher than that of perylene. Interestingly, even-numbered junctions had higher efficiencies than odd-numbered junctions. Nondenaturing gel analyses and fluorescence lifetime measurements demonstrated that the strong odd–even effects were derived from differences in the stability of junctions. The results presented will guide the design of efficient artificial photosynthetic systems. 相似文献