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901.
Zhao Y Slepkov AD Akoto CO McDonald R Hegmann FA Tykwinski RR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):321-329
Monodisperse, cross-conjugated perphenylated iso-polydiacetylene (iso-PDA) oligomers, ranging from monomer 15 to pentadecamer 25, have been synthesized by using a palladium-catalyzed cross-coupling protocol. Structural characteristics elucidated by X-ray crystallographic analysis demonstrate a non-planar backbone conformation for the oligomers due to the steric interactions between alkylidene phenyl groups. The electronic absorption spectra of the oligomers show a slight red-shift of the maximum absorption wavelength as the chain length increases from dimer 17 b to pentadecamer 25, a trend that has saturated by the stage of nonamer 22. Fluorescence spectroscopy confirms that the pendent phenyl groups present on the oligomer framework enhance emission, and the relative emission intensity consistently increases as a function of chain length n. The molecular third-order nonlinearities, gamma, for this oligomer series have been measured via differential optical Kerr effect (DOKE) detection and show a superlinear increase as a function of the oligomer chain length n. Molecular modeling and spectroscopic studies suggest that iso-PDA oligomers (n>7) adopt a coiled, helical conformation in solution. 相似文献
902.
Qing‐Lun Wang Mao Liang Dai‐Zheng Liao Shi‐Ping Yan Zong‐Hui Jiang Peng Cheng 《无机化学与普通化学杂志》2004,630(4):613-616
A unique neodymium(III) complex, {[Nd(BTC)(H2O)4] · H2O}n (BTC = 1, 3, 5‐benzenetricarboxylate), was obtained from the reaction between Nd(ClO4)3 · xH2O and Na3BTC. Coordination bonds, hydrogen bonds, and π‐π stacking form a supramolecular structure with a novel, two‐dimensional framework. The temperature‐dependent magnetic susceptibilities were analyzed by the Curie‐Weiss law; the following values were found C = 1.32, θ = —18.3 K, respectively. 相似文献
903.
Zhao X Chiang CY Miller ML Rampersad MV Darensbourg MY 《Journal of the American Chemical Society》2003,125(2):518-524
The established ability of the Fe(II) bridging hydride species (micro-H)(micro-pdt)[Fe(CO)2(PMe3)]2+, 1-H+, to take-up and heterolytically activate dihydrogen, resulting in H/D scrambling of H2/D2 and H2/D2O mixtures (Zhao et al. Inorg. Chem. 2002, 41, 3917) has prompted a study of simultaneous alkene/H2 activation by such [Fe]H2ase model complexes. That the required photolysis produced an open site was substantiated by substitution of CO in 1-H+ by CH3CN with formation of structurally characterized [(micro-H)(micro-pdt)[Fe(CO)2(PMe3)][Fe(CO)(CH3CN)(PMe3)]]+[PF6]-. Under similar photolytic conditions, H/D exchange reactions between D2 and terminal alkenes (ethylene, propene and 1-butene), but not bulkier alkenes such as 2-butene or cyclohexene, were catalyzed by 1-H+ and the edt (SCH2CH2S) analogue, 2-H+. Substantial regioselectivity for H/D exchange at the internal vinylic hydrogen was observed. The extent to which the olefins were deuterium enriched vs deuterated was catalyst dependent. The stabilizing effect of the binuclear chelating ligands, SCH2CH2CH2S, pdt, and SCH2CH2S, edt, is required for the activity of binuclear catalysts, as the mono-dentate micro-SEt analogue decomposed to inactive products under the photolytic conditions of the catalysis. Reactions of 1 and 2 with EtOSO2CF3 yielded the S-alkylated products, [(micro-SCH2CH2CH2SEt)[Fe(CO)2(PMe3)]2]+[SO3CF3]- (1-Et+), and 2-Et+, rather than micro-C2H5 analogues to the micro-H of 1-H+. The stability and lack of reactivity toward H2 of 1-Et+ and 2-Et+, indicates they are not on the reaction path of the olefin/D2 H/D exchange process. A mechanism with olefin binding to an open site created by CO loss and formation of an Fe-(CH2CHDR) intermediate is indicated. A likely role of a binuclear chelate effect is implicated for the unique S-XXX-S cofactor in the active site of [Fe]H2ase. 相似文献
904.
以脱镁叶绿酸-a甲酯为原料,利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物.镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用,生成了E环被打开的镍(II)δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II)δ-(甲酰乙烯基)二氢卟吩P6三甲酯.镍(II)N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用,生成了镍(II)δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺.当这些化合物脱去镍离子后,吸收波长明显红移,δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742nm.同时保留了对δ-位再进行化学修饰的可能性.合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实. 相似文献
905.
We reported a simple and universal strategy for DNA-mediated assembly of CdTe quantum dots (QDs) and lanthanide-doped upconversion nanoparticles (UCNPs). Such DNA-QD/UCNPs heterostructures not only maintains both fluorescent properties of QDs and upconversion luminescence behaviors of UCNPs, but also offers a polyvalent DNA surface, allowing for targeted dual-modality imaging of cancer cells using an aptamer 相似文献
906.
Xiang Ming He Jian Jun Li Yan Cai Yaowu Wang Jierong Ying Changyin Jiang Chunrong Wan 《Journal of Solid State Electrochemistry》2005,9(6):438-444
A novel process is proposed for synthesis of spinel LiMn2O4 with spherical particles from the inexpensive materials MnSO4, NH4HCO3, and NH3H2O. The successful preparation started with carefully controlled crystallization of MnCO3, leading to particles of spherical shape and high tap density. Thermal decomposition of MnCO3 was investigated by both DTA and TG analysis and XRD analysis of products. A precursor of product, spherical Mn2O3, was then obtained by heating MnCO3. A mixture of Mn2O3 and Li2CO3 was then sintered to produce LiMn2O4 with retention of spherical particle shape. It was found that if lithium was in stoichiometric excess of 5% in the calcination of spinel LiMn2O4, the product had the largest initial specific capacity. In this way spherical particles of spinel LiMn2O4 were of excellent fluidity and dispersivity, and had a tap density as high as 1.9 g cm–3 and an initial discharge capacity reaching 125 mAh g–1. When surface-doped with cobalt in a 0.01 Co/Mn mole ratio, although the initial discharge capacity decreased to 118 mAh g–1, the 100th cycle capacity retention reached 92.4% at 25°C. Even at 55°C the initial discharge capacity reached 113 mAh g–1 and the 50th cycle capacity retention was in excess of 83.8%. 相似文献
907.
制备、表征了混合铝/铬金属氧化物柱撑α-磷酸锆(Al/Cr-ZrP),并对胶体化使用有机胺的种类、柱化液金属离子浓度以及金属离子用量等因素进行了研究。研究表明以乙醇胺为胶体化有机胺比使用正丙胺为胶体化有机胺所得到的产物的层间距更大;采用较低金属离子浓度、较高金属离子用量有利于Al/Cr-ZrP的合成。在Al/Cr比为1、以正丙胺为胶体化有机胺、金属离子浓度为0.067mol·L-1、金属离子用量为6.67CEC的条件下,制备出了混合金属氧化物柱撑α-磷酸锆,其层间距可达3.60nm, 相似文献
908.
909.
910.