类立方烷簇(Et_4N)[MoFe_3S_4(Et_2dtc)_5]CH_3CH的质谱

通过电子轰击谱,并借助亚稳技术及同位素丰度的比较分析,提出了(Et_4N)(MoFe_3S_4(Et_2dtc)-6]·CH_3CN质谱的可能断裂形式指出谱中的三个特征峰m/z 586、500及352的元素组成分别为MoFeS_6C_(14)H_(30)N_3,FeS_8C_(15)H_(30)N_3和FeS_4C_(14)H_(20)N_(20)m/z352的母离子为m/z500,而其子离子为m/z288、276和204。并由这些离子继续裂解成一系列较小的碎片离子。     

2,4-二硫代尿嘧啶的紫外吸收光谱和共振拉曼光谱

硫代嘧啶碱基是光动力疗法潜在的重要光敏剂,其最低单重激发态的光物理研究已有广泛报道。然而,其较高激发态的跃迁性质和反应动力学研究较为稀少。因此,本文采用共振拉曼光谱和密度泛函理论计算方法研究2,4-二硫代尿嘧啶的紫外光谱和几个较高单重激发态的短时结构动力学。首先,基于共振拉曼光谱强度与电子吸收带振子强度f的关系,将紫外光谱去卷积成四个吸收带,分别为358 nm(f=0.0336)中等强度吸收带(A带),338 nm(f=0.1491)、301 nm(f=0.1795)和278 nm(f=0.3532)强而宽的吸收带(B、C和D带)。这一结果既吻合密度泛函理论计算结果,又符合共振拉曼光谱强度模式对紫外光谱带的预期。据此,去卷积得到的四个吸收带被分别指认为S0→S2跃迁、S0→S6跃迁、S0→S7跃迁和S_0→S_8跃迁。同时,分别对B,C和D带共振拉曼光谱进行了详细的指认,获得了短时动力学信息。结果表明,S_8态短时动力学的显著特征是在Franck-Condon区域或附近发生了S8(ππ~*)/S(nπ~*)势能面交叉引发的、伴随超快结构扭转的非绝热过程。S7和S6态短时动力学的主要特征是反应坐标的多维性,它们分别沿C_5C_6/C_2S_8/C_4S_(10)/N_2C_3+C_4N_3H_9/N_1C_2N_3/C_2N_1C_6/C_6N_1H_7/C_5C_6H_(12)和C_5C_6/N_3C_2/C_4S_(10)/C_2S_8+C_6N_1H_7/C_5C_6H_(12)/C_5C_6N_1/C_5C_6H_(12)/C_2N_1C_6/N_1C_2N_3/C_4N_3H_9/N_1C_2N_3等内坐标演化。     

SYNTHESIS AND STRUCTURE OF Cu(Ⅱ)COMPLEXES BY OXIDATIVE ADDITION OF DIBENZOYL PEROXIDE ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copperpowder with 2,2′-bipyridine(or imidazole)in a mixed solvent(methanol andtetrahydrofuran),and affords the Cu(Ⅱ)complexes-[Cu(Ce(C_6H_5COO)_2(2,2'-bipy)]H_2O(1)and[Cu(C_6H_5COO)_2(C_3H_4N_2)_2](2).The structure was solved by direct methodsand Fourier synthesis.C_(24)H_(20)N_2O_5Cu (1),Mr=479.78,space group P2(1)/c,a=6.986(7),b=18.833(I),c=17.021(3),α=γ=90°,Z=4,V=2218.1~3,Dc=1.443g/cm\+3,R=0.055Rw=0.062.Complex(2),C_(20)H_(18)N_4O_4Cu(2),Mr=441.74,space group P2(1)/n,a=8.699(4),b=9.840(6),c=12.399(5),α=γ=90°,β=100.8°,Z=4,V=1010.9~3,Dc=1.654g/cm\+3,R=0.055,Rw=0.062.     

2,3—二氢—5,6—二苯基吡嗪及其2∶1硝酸银配合物的合成与晶体结构

合成了配体2,3-二氢-5,6-二苯基吡嗪(C_(16)H_(14)N_2)及其硝酸银配合物AgNO_3(C_(16)H_(14)N_2)_2, 并用CAD4衍射仪测定了它们的晶体结构。晶体学数据为, 配体C_(16)H_(14)N_2: 单斜晶系, 空间群P2_1/n, a=0.5685(3),b=0.7928(1), c=2.7261(8) nm, β=95.02(6)°, V=1.2287 nm, z=4,D_c=1.27gcm~(-3),μ=0.81cm~(-1),R=0.031, R_w=0.033; 配合物AgNO3(C_(16)H_(14)N_2)_2:单斜晶系, 空间群A2, a=0.5655(3), b=0.7771(2), c=3.0.502(5) nm, β=94.90(2)°, V=1.3355 nm, z=2, D_c=1.59gcm~(-3),μ=7.87cm~(-1), R=0.033, R_2=0.028。测定结果表明, 在C_(16)H_(14)N_2分子中, 有关键长、键角均符合相应正常值。在AgNO3(C_(16)H_(14)N_2)_2晶体中NO_3~-为双齿配体; C_(16)H_(14)N_2则因吡嗪环上苯基的空间障碍而作为单齿配体出现; Ag原子处于二重轴上, 周围由四个氧和两个氮原子组成严重扭曲的配位八面体; Ag(1)—O(1)键长为2.828, Ag(1)—O(2)为2.520, Ag(1)—N(31)为0.2399 nm. Ag的配位八面体间借公用相对两个顶点氧原子而构成无限链状结构.     

若干环戊二烯基(N,N-二苄基氨荒酸)锆衍生物的质谱研究

本文通过电子轰击谱,并借助于同位素丰度分析和亚稳跃迁数据,阐述了标题衍生物(MeCp)Zr(S_2CN(C_7H_7)_2)_3(Ⅰ)、CpZr(S_2CN(C_7H_7)_2)_3(Ⅱ)、(MeCp)_2ZrCl(S_2CN(C_7H_7)_2)(Ⅲ)和Cp_2ZrCl(S_2CN(C_7H_7)_2)(Ⅳ)的质谱断裂途径。对于配合物(Ⅰ)和(Ⅱ),可看到从分子离子中首先丢失N,N-二苄基氨荒酸配体或该配体的部分碎片离子(C_7H_7~+),构成两个配合物的主要断裂途径。而丢失Cp或MeCp配体,在两种配合物质谱中则有差别。一般地说,Cp较MeCp易于丢失。这可能由于MeCp比Cp有较强给电子能力,因而使配体与金属间键得以加强。对于配合物(Ⅲ)和(Ⅳ),上述关系不明显。在配合物(Ⅳ)中,通过同位素丰度分析,指明m/z 462和m/z 463两种不同离子组成的两簇峰相互重叠,构成观察到的一簇叠加同位素峰。     

氮杂冠醚研究——Ⅲ.N-取代苯并氮杂冠醚的质谱研究

本文报道两种单取代苯并氮杂冠醚(1)和四种双取代苯并氮杂冠醚(2)的电子轰击(EI)质谱及其分子离子峰。化合物(1)的特征峰,m/z 372,342,236,192,136,121,109,56;化合物(2)的特征峰:m/z[M-109]~ ,[M/2]~ ,[M/2±13]~ 等。据此提出了单取代和双取代苯并氮杂冠醚经电子轰击断裂的可能途径。     

二茂铁衍生物的合成、表征及猝灭Ru(bpy)_3~(2+)发光的研究

本文以邻菲罗啉和二茂铁为原料,合成了一系列新Schiff碱型二茂铁衍生物:(C_(10)H_6N_2)C=N—N=CR—Fe,(C_(10)H_6N_2)C=N—C_6H_4—N=CR—Fe,(C_(10)H_6N_2)C=N—C_6H_4—C_6H_4—N=CR—Fe,(R=H,CH_3,Fe为二茂铁基);并对其进行了元素分析和光谱表征.该类二茂铁衍生物能有效地猝灭Ru(bPY)_3~(2+)的发光,Stern-Volmer图呈线性关系,双分子猝灭过程速率常数k_q为10(?)dm~3/mol·s~(-1)数量级.猝灭过程按电子转移还原机理进行.     

三重桥氧三核铁脂肪酸配合物FAB和EI质谱研究

本文报道三重桥氧三核铁脂肪酸配合物[Fe_3(μ_3～O)(μ-O_2CR)_6(H_2O)]_3~+(R=CH_3,C_2H_5,C_3H_7,C_4H_9,C_(15)H_(31)和C_(17)H_(35))的快原子轰击(FAB)和电子轰击(EI)质谱。在FAB—MS谱中观察到四种系列离子:Ⅰ.[Fe_3O(O_2CR)_n]~+n=2-6;Ⅱ.[Fe_3O(O_2CR)_nO]~+n=1-4;Ⅲ.[Fe_2O(O_2CR)_n]~+n=1-3;Ⅳ.[Fe_2(O_2CR)_n]~+n=2-4;以及与底物所形成的加合离子[Fe_3O(O_2CR)_n·NBA-1]~+n=3-5(NBA是间-硝基苄醇)。在EI—MS谱中,除上述Ⅰ—Ⅳ离子(其中n的数目略有差异)外,还观察到含三个配位水的完整阳离子[Fe_3(O_2CR)_6(H_2O)_3]~+及其与配体羧酸的加合离子[Fe_3O(0_2CR)_n(H_20)_3·RCOOH+H]~+n=4-6,(Fe_3O(O_2CR)_nO(H_2O)3·RCOOH+H]~+n=2—4和Fe(O_2CR)_n]~+n=1—3。分析了它们的断裂规律,探讨了从中所获得的有益启示。     

Dimensional effects of organic anion templates in modulating the assembly of water clusters in cucurbit[6]uril supramolecular systems

Two new supramolecular architectures {(HC_2O_4)_22 [C_6H_(18)N_22+ C_(36)H_(36)N_(24)O_(12)]} 12H_2O(1) and{(C_6H_5SO_3)_22 [C_6H_(18)N_22+ C_(36)H_(36)N_(24)O_(12)]} 12H_2O(2) were synthesized and characterized by singlecrystal X-ray diffraction, thermogravimetric analysis and X-ray powder diffraction. Compound 1contains infinite two dimensional(2D) L18(8)14(8)8(4) type anion–water aggregates [(HC_2O_4)_4(H_2O)_(22)]~4 and results in the construction of sandwich-like three dimensional(3D) networks. In compound 2, honeycomb-like three dimensional(3D) networks are fabricated by one dimensional(1D)‘‘W'-like T5(0)A2 type anion–water clusters [(C_6H_5SO_3)(H2O)6]. These results indicate that anionic groups play a crucial role in modulating the structures of water clusters with their spatial structure and binding sites. In these two structures, the majority of interactions are O...H and H...H interactions on the Hirshfeld surface, which means that hydrogen bonding and hydrophobic interactions are the dominate drive forces in forming these supramolecular systems.     

两个基于多金属氧酸盐和水杨醛缩氨基硫脲的有机-无机杂化配合物的合成与晶体结构

采用自然蒸发法,合成了2个新颖的有机-无机杂化配合物[C_8H_6N_3S]_2[H_2Mo_2O_7](1)和[CoⅡ(C_8H_8N_3OS)_2]_2[H_3PW_(12)O_(40)]·4DMF(2),并对其进行了元素分析、IR、TG和单晶X-射线衍射表征.结果表明:化合物1是由1个双核多阴离子[H2Mo2O7]2-与2个有机组分[C_8H_6N_3S]+通过共价键形成的一维链状结构;化合物2是由水杨醛缩氨基合钴与DMF分子及多酸阴离子通过氢键作用形成的三维网状结构,其中水杨醛缩氨基硫脲合钴呈风车型.     

锂离子电池正极材料LiFePO4的结构与电化学性能的研究

利用固相法和球化工艺合成了橄榄石型LiFePO4粉体.该粉体由直径为10-15μm的团簇体组成.以合成材料为正极的锂离子电池的循环伏安特性表明,在循环过程中,锂离子插入和脱出具有单一的可逆机制.在不同温度下,材料的交流复阻抗谱表明,随着温度的升高,电池电化学阻抗明显减小.充放电测试结果表明,在17mA/cm2的电流密度下,材料工作电压平稳,电极极化效应较小,容量接近其理论值.在170mA/cm2的电流密度下,电池容量没有明显的减小趋势,而在170mA/cm2电流密度以上时,电池容量迅速降低,且电极极化效应比较显著.经过较大的电流密度测试后,材料在小电流密度下仍然保持着接近理论容量的循环容量.     

稀土元素与L-酪氨酸和甘氨酸三元固态配合物的合成及表征

目前稀土与氨基酸三元固态配合物的研究着重于少数稀土-氨基酸-非氨基酸类型.本文报道了10种稀土与L-酪氨酸(Tyr,HO——CH_2(NH_2)CHCOOH)和甘氨酸(Gly,NH_2CH_2COOH)三元固态配合物的合成及FTIR光谱、质谱表征.     

CdSe纳米晶/共轭聚合物太阳电池的制备与性能研究

采用有机金属液相法制备了平均粒径为5 nm的CdSe纳米微球(ns-CdSe), 并将其与共轭聚合物(MEH-PPV或P3HT)共混制备了太阳电池器件. 透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)及荧光光谱(PL)研究结果表明, CdSe纳米晶呈均匀的球状颗粒, 在近红外区具有良好的吸收和荧光性能; 加入CdSe纳米晶能够有效地淬灭共轭聚合物的荧光. 在AM1.5模拟太阳光(光强为100 mW/cm2)照射下, ns-CdSe/MEH-PPV共混体系太阳电池器件性能测试结果为: 短路电流ISC为1.56 mA/cm2, 开路电压VOC为0.75 V, 填充因子FF为34.5％, 光电转换效率η为0.40%; 对于ns-CdSe/P3HT共混体系, 其ISC为1.93 mA/cm2, VOC为0.65 V, FF为38.4%, η为0.48%.     

Thermochemistry of the activation of N2 on iron cluster cations: Guided ion beam studies of the reactions of Fe(n)+ (n = 1-19) with N2

The kinetic energy dependences of the reactions of Fe(n)+ (n = 1-19) with N2 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-15 eV. In addition to collision-induced dissociation forming Fe(m)+ ions, which dominate the product spectra, a variety of Fe(m)N2+ and Fe(m)N+ product ions, where m < or = n, is observed. All processes are observed to exhibit thresholds. Fe(m)+ - N and Fe(m)+ - 2N bond energies as a function of cluster size are derived from the threshold analysis of the kinetic energy dependences of the endothermic reactions. The trends in this thermochemistry are compared to the isoelectronic D0(Fe(n)+ - CH), and to bulk phase values. A fairly uniform barrier of 0.48+/-0.03 eV at 0 K is observed for formation of the Fe(n)N2+ product ions (n = 12, 15-19) and can be related to the rate-limiting step in the Haber process for catalytic ammonia production.     

Sulfurization of polymers. 6. Poly(vinylene polysulfide), poly(thienothiophene), and related structures from polyacetylene and elemental sulfur

Polyacetylene obtained by the dehydrochlorination of polyvinyl chloride in the NaOH—DMSO system undergoes sulfurization with elemental sulfur at 120—300 °C to liberate hydrogen sulfide and to form electroconducting (0.7·10^–12—5.8·10^–15Sm nm^–1) and paramagnetic (1.5·10¹⁷—1.7·10¹⁹sp g^–1, g = 2.0035—2.0045, H= 0.44—0.66 mT) dark powders with a metallic luster. Their IR spectra and comparison with the samples of sulfurized polyethylene show that sulfurized polyacetylene contains poly(vinylene polysulfide), poly(thienothiophene), and related structures. The polymers afford the cathode discharge capacity of lithium batteries up to 950 mA h g^–1(in the first cycle) and stable cycling at a level of 500—300 mA h g^–1(25 cycles).     

Variable-temperature 19F NMR and theoretical study of 1,9- and 1,7-C60F(CF3) and C(s-) and C1-C60F17(CF3): hindered CF3 rotation and through-space J(FF) coupling

Milligram amounts of the new compounds 1,9- and 1,7-C60F(CF3) (ca. 85:15 mixture of isomers) and C60F3(CF3) were isolated from a high-temperature C60/K2PtF6 reaction mixture and purified to 98 mol % compositional purity by two-dimensional high-performance liquid chromatography using Buckyprep and Buckyclutcher columns. The previously observed compounds C60F5(CF3) and C60F7(CF3) were also purified to 90+ mol % for the first time. Variable-temperature 19F NMR spectra of the mixture of C60F(CF3) isomers and the previously reported mixture of C(s)- and C1-C60F17(CF3) isomers demonstrate for the first time that fullerene(F)n(CF3)m derivatives with adjacent F and CF3 substituents exhibit slow-exchange limit hindered CF3 rotation spectra at -40 +/- 10 degrees C. The experimental and density functional theory (DFT) predicted deltaH++ values for CF3 rotation in 1,9-C60F(CF3) are 46.8(7) and 46 kJ mol(-1), respectively. The DFT-predicted deltaH++ values for 1,7-C60F(CF3), C(s)-C60F17(CF3), and C1-C60F17(CF3) are 20, 44, and 54 kJ mol(-1), respectively. The (> or = 4)J(FF) values from the slow-exchange-limit 19F spectra, which vary from ca. 0 to 48(1) Hz, show that the dominant nuclear spin-spin coupling mechanism is through-space coupling (i.e., direct overlap of fluorine atom lone-pair orbitals) rather than coupling through the sigma-bond framework. The 2J(FF) values within the CF3 groups vary from 107(1) to 126(1) Hz. Collectively, the NMR data provide an unambiguous set of (> or = 4)J(FF) values for three different compounds that can be correlated with DFT-predicted or X-ray diffraction derived distances and angles and an unambiguous set of 2J(FF) values that can serve as an internal standard for all future J(FF) calculations.     

Synthesis, structural characterization, and electrophosphorescent properties of rhenium(I) complexes containing carrier-transporting groups

Two novel diimine rhenium(I) carbonyl complexes with the formula [Re(CO)(3)(L)Br], where L = 1-(4-5'-phenyl-1,3,4-oxadiazolylbenzyl)-2-pyridinylbenzoimidazole (1) and 1-(4-carbazolylbutyl)-2-pyridinylbenzoimidazole (2), have been successfully synthesized and characterized by elemental analysis, (1)H NMR, and IR spectra. Their electrochemical, photophysical, and electroluminescent behaviors, along with the X-ray crystal structure analysis of 2, are also described. White electrophosphorescent devices were fabricated using 1 and 2 as emitters. The devices based on carbazole-containing (hole-transporting group) 2 with the structure ITO/m-MTDATA (30 nm)/NPB (20 nm)/2:CBP (8%, 30 nm)/Bphen (20 nm)/Alq(3) (20 nm)/LiF (0.8 nm)/Al (200 nm) exhibit Commission Internationale de L'Eclairage coordinates of x = 0.34, y = 0.33 with a maximum brightness of 2300 cd/m(2) at 580 mA/cm(2). When a brightness of 1500 cd/m(2) appears at 230 mA/cm(2), the devices based on 10 wt % 2 still possess 56% of the maximum efficiency which appeared at 2.7 mA/cm(2). These performances are among the best reported for devices using Re(I) complexes as emitters. By comparison of the electroluminescent properties of the devices based on 1 and 2, we conclude that the introduction of the carbazole group into the ligand improves the performance of 1-doped devices.     

CO LMR spectrum of ~(14)N~(16)O and its analysis with spectra of ~(14)N~(17)O and ~(14)N~(18)O

LMR spectra for v=1←0 transitions of 14N16O in X2Π1/2,3/2 states were observed at 5.6 μm and 5.4 μm of CO laser. Introducing the advanced isotopic molecular constant scaling function to Hund's case (a) diatomic structure model, these spectra were analyzed and fitted together with all reliable previous spectral data of 14N16O as well as 14N17O and 14N18O. A full set of precise molecular parameters and their vibrational dependencies have been determined with much higher precision (1 -2 orders for most parameters). Many of them have been obtained for the first time. Using isotopic scaling function, the molecular constants of 14N17O and 14N18O were deduced.     

C6, C7, and C8 perfluoroalkyl-substituted phosphinic acids

Reaction of red phosphorus with RfI in a 1:2 molar ratio at 230 degrees C led to the formation of a mixture of (Rf)2PI and (Rf)PI2 (Rf = C6F13, C7F15, C8F17) in about a 70:30 ratio, respectively. These mixtures were separated by vacuum distillation. (Rf)2PI (Rf = C6F13, C7F15) are yellow liquids whereas (C8F17)2PI is a yellow solid. Oxidation of (Rf)2PI with excess NO2 led to (Rf)2P(O)OH (Rf = C6F13, C7F15, C8F17) in > 90% isolated yields after aqueous hydrolysis of the anhydride intermediates. These highly fluorinated phosphinic acids are white solids with sharp melting points and are highly soluble in methyl sulfoxide (DMSO) and 1,1,2-trichlorotrifluoroethane. However, solubility in chloroform and methylene dichloride is low. These perfluoroalkylphosphinic acids were characterized by IR, NMR (1H, 19F, and 31P), and mass spectra and elemental analysis.     

Calix[4]arenes with siloxanes bridging opposite rings

Several C-silylated (allyldimethylsilyl) calixarenes (1, 14, and 18) were treated with commercial TBAF in THF, giving the novel calixarenes 2, 15, and 19, in which the opposite rings were bridged by a Si-O-Si siloxane group. Compound 19 and the derived phenol 20 (as well as the dibromocalixarene precursor 17) were mixtures of cone and partial cone conformations according to NMR, while 2 and 15 (as well as 14 and the cone components of 17, 19, and 20) were in flattened cone conformations.