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991.
992.
以电化学和现场紫外-可见-近红外及现场FTIR光谱电化学方法对Dawson结构杂多阴离子[HAS2Mo18O62]5-在非质子介质(CH3CN)中的电还原过程进行了研究.结果表明,该杂多阴离子在非质子介质中经历4步单电子还原反应,所产生的杂多蓝阴离子在近红外区出现宽广的价间电荷转移吸收带,而红外区Mo=O端键及Mo—O—Mo桥键的特征吸收峰在还原后均有不同程度的红移. 相似文献
993.
ZHENG Yan YANG Bing ZHANG Hai-quan LU Ping SHEN Fang-zhong LIU Lin-lin XU Hai YANG Guang-di MA Yu-guang 《高等学校化学研究》2007,23(6):720-725
A soluble poly(meta-phenylene)derivative with rigid twisted biphenyl unit was synthesized by the Yamamoto coupling reaction.The polymer is soluble in common organic solvents,and the number-average molecular weight is about 6500.The UV-Vis and quantum chemical calculation indicate that the different conformation segments named "conformers" exist in the polymer backbones;it was also further confirmed by the single crystal X-ray diffraction study of the dimeric model compound.The π-π transition of biphenyl segments of twisted and planar conformations made the polymer exhibit a strong absorption around 256 nm and a weak absorption at about 300 nm.Furthermore,the polymer exhibits a strong UV photoluminescence at 372 nm when the excitation wavelengths are longer than 300 nm.The ultraviolet-emitting electroluminescence(EL)device with the single layer structure shows EL λmax of the derivative at 370 nm. 相似文献
994.
通过氧吸附量、噻吩吸附热及反应速率常数的测定,研究了MoO3/MCM-41、MoO3-CoO(NiO)/MCM-41系列催化剂,发现,对于MoO3/MCM-41催化剂,当MoO3的质量分数(以MCM-41为底数,即MCM-41=1g时,MoO3含量为0.15g,下同)从15%增加到20%时,其噻吩的加氢硫(HDS)活性增大,至25%时活性下降,所对应的氧吸附量(mL/g催化剂)也是先增大后减少,并且两者有很好的线性对应关系,而且噻吩吸附热则基本保持不变,采用不同的MoO3-CoO(NiO)浸渍顺序制备的MoO3-CoO(NiO)/MCM-41催化剂中,先浸渍CoO(NiO)再浸渍MoO3的催化剂,其噻吩HDS活性明显优于对其它浸渍顺序制备的催化剂,同时催化剂的氧吸附量和噻吩吸附热也最大。 相似文献
995.
Several imidazo[4,5-d]pyridazine nucleosides which are structurally similar to inosine were synthesized. Anhydrous stannic chloride-catalyzed condensation of persilylated imidazo[4,5-d]-pyridazin-4(5H)one (1) and imidazo[4,5-d]pyridazine-4,7(5H,6H)dione ( 16 ) with 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranose ( 3 ) provided (after sodium methoxide deblocking) 6-β-D-ribo furanosylimidazo[4,5-d]pyridazin-4(5H)one (5) and 3,6-di-(β-D-ribofuranosyI)imidazo[4,5-d]pyridazin-4-one ( 7 ); and 1-(β-D-ribofuranosyl)imidazo[4,5-d]pyridazine-4,7(5H,6H)dione ( 19 ) and 1,5 or 6-di-(β-D-ribofuranosyl)imidazo[4,5-d ]pyridazine-4,7(5H or 6H)dione ( 21 ), respeeitvely. 4,7-Diehloro-1-β-D-ribofuranosylimidazo[4,5-d]pyridazine ( 12 ) and dimethyl 1-β-D-ribofuranosylimidazole-4,5-dicarboxylate ( 26 ), both prepared from stannic chloride-catalyzed ribosylations of the corresponding heterocycles, were converted in several steps to 3-β-D-ribo-furanosy limidazo[4,5-d]pyridazin-4(5H)one ( 14 ) and nucleosidc 19 , respectively. Acid-catalyzed isopropylidenation of mesomeric betaine 7 or nuclcoside 14 provided 3-(2,3-isopropylidene-β-D-ribofuranosyl)imidazo[4,5-d]pyrizin-4(5H)one ( 31 ). 1-β-D-Ribofuranosylimidazo[4,5-d]-pyridazine ( 29 ) was obtained in several steps from nueleoside 12 . The structure of the nucleosides was established by the use of carbon-13 and proton nmr. 相似文献
996.
3-Dcazacytosine (4-amino-2-pyridone, 3 ), 3-doazauracil (4-hydroxy-2-pyridone, 5 ), 3-deaza-cytidine (4-amino-1-β-D-ribofuranosyl-2-pyridonc, 9 ), and 3-deazauridine (4-hydroxy-1-β-D-ribo-furanosyl-2-pyridone, 11 ) were prepared in high overall yields from 1-methoxy-1-buten-3-yne ( 1 ). Ethyl 3,5,5-triethoxy-3-pentenoate ( 2 ), obtained from acylatioti of 1 with diethyl carbonate and subsequent in situ conjugate addition of ethoxide, was cyelized with ammonia to provide 3 . Diazotization of 3 and subsequent in situ hydroxydediazotization afforded 5 . Nucleoside 9 was obtained from the stannic chloride-catalyzed condensation of bis-trimethylsilylated 3 and 1-O-acetyl-2,3,5-tri-O-benzoyl-β-D-ribofuranose ( 7 ), followed by ammonolysis of the blocking groups. Diazotization of 9 and subsequent in situ hydroxydediazotization afforded nucleosidc 11 . 相似文献
997.
998.
The crystal of [Co(H2O)6]·(Hnip)2·(H2nip)2·(OMA)2·(H2O)8 has been cultured using direct method and characterized by X-ray single crystal diffractometry, elemental analysis and FTIR spectroscopy. It crystallizes in triclinic system, P-1 space group with the cell parameters of a=0.7012(1) nm, b=1.1378(2) nm, c=1.6612(3) nm, α= 84.92(3)°, β=85.19(3)°, γ=85.91(3)°, V= 1.3128(5) nm^3, Z=1, Dc= 1.573 g·cm^-3. Final R indices [1〉2σ(I)] are: R1 =0.0279, wR2=0.0765 while R indices for all data are: R1 =0.0327, wR2=0.0806. The Co coordination octahadra are each surrounded by two Hnip, two H2nip, two DMA and eight water molecules that are linked by hydrogen bonds and π-π stacking interactions. Thermal analyses of DSC and TG-DTG have been performed on the complex to predict its thermal decomposition mechanism and determine the most probable kinetic model function using Kissinger, Ozawa, integral and differential methods. 相似文献
999.
Self-assembled monolayers (SAMs) of n-butanethiol, n-dodecanethiol and their equimolar mixture on Au(111) were prepared and characterized by ellipsometry, contact angle measurement, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results revealed that these SAMs are oriented ultrathin films with the thickness of nanometer scale, and the SAMs were influenced by the molecular chain length, the lattice orientation and cleanliness of the substrates. The surface of the longer chain SAM is hydrophobic. The thicknesses of three SAMs of n-butanethiol, n-dodecanethiol and their mixture revealed by ellipsometry and XPS are about 0.59 - 0.67nm, 1.60- 1.69 nm and 1.23 - 1.32nm, respectively. AFM images further demonstrated that the SAM formed by the mixture has some microdomains with two different thicknesses. 相似文献
1000.
Comparative investigation on non-IPR C68 and IPR C78 fullerenes encaging Sc3N molecules 总被引:2,自引:0,他引:2
A computational study on the experimentally detected Sc(3)N@C(68) cluster is reported, involving quantum chemical analysis at the B3LYP/6-31G level. Extensive computations were carried out on the pure C(68) cage which does not conform with the isolated pentagon rule (IPR). The two maximally stable C(68) isomers were selected as initial Sc(3)N@C(68) cage structures. Full geometry optimization leads to a confirmation of an earlier assessment of the Sc(3)N@C(68) equilibrium geometry (Nature 2000, 408, 427), namely an eclipsed arrangement of Sc(3)N in the C(68) 6140 frame, where each Sc atom interacts with one pentagon pair. From a variety of theoretical procedures, a D(3h) structure is proposed for the free Sc(3)N molecule. Encapsulated into the C(68) enclosure, this unit is strongly stabilized with respect to rotation within the cage. The complexation energy of Sc(3)N@C(68) cage is found to be in the order of that determined for Sc(3)N@C(80) and exceeding the complexation energy of Sc(3)N@C(78). The cage-core interaction is investigated in terms of electron transfer from the encapsulated trimetallic cluster to the fullerene as well as hybridization between these two subsystems. The stabilization mechanism of Sc(3)N@C(68) is seen to be analogous to that operative in Sc(3)N@C(78). For both cages, C(68) and C(78), inclusion of Sc(3)N induces aromaticity of the cluster as a whole. 相似文献