Facile formation of five-membered N-heterocyclic zirconacycloallenoids

The reaction of η(2)-iminozirconocene chloride complexes with trimethylsilylethynyl lithium leads to rapid C-C coupling at room temperature to yield the corresponding five-membered aza-zirconacycloallenoids. Such compounds were also obtained by trapping of in situ generated zirconocene with alkynyl imines.     

Synthesis,Crystal Structures,and Properties of 6,12‐Diaryl‐Substituted Indeno[1,2‐b]fluorenes

Fused polycyclic indeno[1,2‐b]fluorene derivatives with aryl substituents at the 6,12‐positions have been prepared as a potential antiaromatic 20π electronic system. They showed strong absorptions in the visible region and amphoteric redox properties. The quinoid‐type molecular structures were revealed by X‐ray crystal‐structure analysis, which indicated that the bond lengths of the quinoid unit depend on the aryl substituents. Whereas nucleus‐independent chemical shift NICS(1) calculations indicate the antiaromatic nature of the s‐indacene core, they have higher stability than substituted acene derivatives. The derivatives with difluorophenyl or anthryl groups were stable in solution. Vapor‐deposited thin films showed ambipolar carrier transportation in the field‐effect transistor devices.     

电阻式核磁共振测量的最新进展

电阻式核磁共振(RDNMR)测量是1988年由德国马普所的von Klitzing研究小组针对GaAs二维电子气中少量核自旋的探测而提出的一种具有超高灵敏度的实验技术. 目前, RDNMR已经成为研究单层或双层GaAs二维电子气核自旋和电子自旋特性的重要手段. 由于为实现电阻式核磁共振测量所建立的动态核极化方法强烈依赖于GaAs特有的材料属性, 至今这一技术一直没有扩展应用到其他半导体低维系统中. 最近,本研究小组发展了一种动态核极化新方法,成功实现了对典型窄带半导体锑化铟(InSb) 二维电子气的电阻式核磁共振测量.本文在介绍电阻式核磁共振测量工作原理及已建立的典型动态核极化方法的基础上,着重讨论所提出的动态核极化新方法的机理、 实验结果以及对今后研究的展望.     

Total synthesis of COPD biomarker desmosine that crosslinks elastin

Desmosine, a crosslinking amino acid of elastin, is an attractive biomarker for diagnosis of chronic obstructive pulmonary disease (COPD). In this study, the first total synthesis of (+)-desmosine was achieved in 11% overall yield in 13 steps utilizing stepwise and regioselective Sonogashira cross-coupling reactions.     

Studies on the mechanism for stereoisomerization of 1-zirconacyclopent-3-yne compounds

The stereoisomerization of 2,5-disubstituted 1-zirconacyclopent-3-yne compounds, stable five-membered cycloalkynes, has been studied with regard to the mechanism. The bimetallic complex of 1,4-bis(trimethylsilyl)butatriene was synthesized and structurally characterized, although it seems unimportant for the stereoisomerization reactions. The isomerization of trans-1,1-bis(η⁵-cyclopentadienyl)-2,5-bis(trimethylsilyl)-1-zirconacyclopent-3-yne 2a into the cis-form in benzene-d₆ solution were observed using ¹H NMR spectroscopy at 50 °C in various concentrations. The reaction was first order with respect to trans-2a. This ruled out the possibility that a bimetallic complex was responsible for the isomerization. A kinetic isotope effect was observed (k_H/k_D = 1.8), suggesting that C–H activation is involved in the rate-determining step. A mechanism via hydrogen elimination from the complex of η⁴-π,π-coordination mode is proposed.     

Linear hydrogen‐bonded molecular tapes in the cocrystals of squaric acid with 4,4′‐dipyridylacetylene and 1,2‐bis(4‐pyridyl)ethylene

The title compounds, 4,4′‐(ethyne‐1,2‐diyl)­dipyridinium bis(squarate), C₁₂H₁₀N₂²⁺·2C₄HO₄^?, and 4,4′‐(ethene‐1,2‐diyl)­dipyridinium bis­(squarate), C₁₂H₁₂N₂²⁺·2C₄HO₄^?, are isomorphous and crystallize in space group P. The cocrystals contain linear hydrogen‐bonded molecular tape structures along the [120] direction. The squarate monoanions form a ten‐membered dimer linked by two intermolecular O—H?O hydrogen bonds. Each component mol­ecule forms a segregated stack along the c axis. The bond lengths of the squarate monoanion indicate delocalization of the enolate anion.     

A mol­ecule with a C1‐homobasketane framework

The title compound, 6‐(1,3‐benzodi­thiol‐2‐yl­idene)‐5,7‐di­methyl‐1,2‐di­phenylpenta­cyclo­[5.4.0.0^2,5.0^3,11.0^4,8]­un­decane, C₃₂H₂₈S₂, with a C₁‐homobasketane framework, crystallizes in the P space group with one mol­ecule in the asymmetric unit. The two cyclo­butane rings in the cage are in a puckered conformation. Due to the enhanced through‐bond interaction of the phenyl π systems involving a strained σ bond, the (Ph—­)C—C(—Ph) bond length is significantly extended, to 1.610 (3) Å.     

4,7‐Bis(4‐pyridyl­ethynyl)‐2,1,3‐benzo­thia­diazo­le and its dipyridinium diperchlorate

The title compound, C₂₀H₁₀N₄S, and its dipyridinium salt, 4,4′‐(2,1,3‐benzo­diazol‐4,7‐diyl­diethynyl)­dipyridinium diperchlorate, C₂₀H₁₂N₄S²⁺·2ClO₄^?, display bond alternation in the 2,1,3‐benzo­thia­diazo­le rings, which suggests their quinonoid character. The dipyridinium dication mol­ecules stack along the a axis and form a dimer with short S?N interheteroatom contacts [3.146 (4) Å] between the two 1,2,5‐thia­diazo­le rings. The dimer is surrounded by the perchlorate anions with which it forms a large number of intermolecular N—H?O and C—H?O hydrogen bonds.     

Multiple Phase Transitions in CuO Studied by μSR

Precise measurements of the local magnetic field at muon sites in CuO were performed. The temperature dependence of the local field including spatial orientation was obtained in the ordered state. Not only zero field μSR measurements were performed, but also external magnetic fields were applied to obtain an unambiguous determination of field direction. Multiple stages of muon signals were observed at 55 and 80 K. An incommensurate phase between 212 K and 227 K was confirmed from the line shapes of the local fields at the muon sites. This revised version was published online in September 2006 with corrections to the Cover Date.     

Improvement of thermochromic property at low temperatures of CuMo0.94W0.06O4 by Zn substitution

Zinc-doped copper molybdenum oxide, Zn-doped CuMo_0.94W_0.06O₄, was synthesized, and the effects of the Zn doping on the thermochromic property of CuMo_0.94W_0.06O₄ were investigated at low temperatures. X-ray diffractometry and diffuse reflectance UV–Vis spectroscopy clarified that Zn doping for CuMo_0.94W_0.06O₄ promoted the structural phase transition of the γ-phase to the α-phase of CuMo_0.94W_0.06O₄ at low temperatures and Zn-doped CuMo_0.94W_0.06O₄ exhibited a drastic color change in the temperature range of 30–70 °C. Differential scanning calorimetry also confirmed that Zn doping changed the phase transition temperature of CuMo_0.94W_0.06O₄. Consequently, Cu_1?xZn_xMo_0.94W_0.06O₄ with x?=?0.01 exhibited a larger thermal change in the diffuse reflectance spectrum in the visible light range, compared with CuMo_0.94W_0.06O₄. An appropriate Zn-doping ratio was effective for enhancing the thermochromic property of the CuMo_0.94W_0.06O₄ pigment in the visible region in the temperature range of 30–70 °C.