Poly-5,10,15,20-tetrakis(4-hydroxyphenyl)porphyrin as a material for photovoltaic devices

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裸露金属簇状化合物K_4Pb_xSn_(9-x)的~(119)Sn、~(207)Pb多核核磁共振研究

本文对乙二胺溶液中裸露金属原子簇用~(119)Sn及~(207)Pb核磁共振作了研究。对每个峰做了标识。根据谱线强度进行分析,得知溶液中锡与铅的比例大于固体中的比例。从自由能的角度看,Pb_2Sn_7~(4-)是最不稳定的一种原子簇,本文还对谱线中各条线都进行了理论拟合,结果与实验相吻合。     

Synthesis and Crystal Structure of an Ion- pair Compound: [HL]_2[Ni(CN)_4]·4H_2O (L = 4-(2- Hydroxyphenyl)-1,5, 9-triazacyclododecan-2-one)

1INTRODUCTIONCyclicpolyamineshaveoriginatedagreatdealofinterestowingtotheirbiologicalactivity[1～3]andalotofmetalcomplexeswithmacrocyclicpoly-amineligandssuchastriamine[12]aneN4,tetra-aminecyclen,cyclam,pentaamine[16]aneN5,theirderivativesandsoonhavebeens…     

表面活性剂对Al2O3吸附MoO4^2—的影响

土壤自溶液中吸附MoO_4~(2-)会影响植物生长。前人对这一吸附过程已作过一些研究。本文报导阴离子表面活性剂十二烷基硫酸钠(SDS),阳离子表面活性剂氯化十六烷基吡啶(CPC)和非离子表面活性剂吐温-20(TW-20)对Al_2O_3吸附MoO_4~(2-)的影响。 实验所用吸附剂为层析用中性Al_2O_3(上海五四农场化学试剂厂),SDS(化学纯,广东石岐化工厂),CPC(化学纯。上海试剂一厂),TW—20(试剂级),其余试剂均为分析纯,含钼液用Na_2MoO_4配制。     

Nucleophilic difluoromethylation and trifluoromethylation using tetrakis(dimethylamino)ethylene (TDAE) reagent

In an effort to find new methodologies to introduce difluoromethylene and trifluoromethyl moieties into organic molecules of synthetic and biological interest, tetrakis(dimethylamino)ethylene (TDAE) was found to be an effective reductant of a series of good electron-acceptors such as bromodifluoromethyl heterocycles, chlorodifluoromethylated ketones as well as perfluoroalkyl iodides; the corresponding anions thus generated under very mild conditions, were successfully engaged in a number of intra- and intermolecular coupling reactions with a series of electrophiles (aldehydes, ketones, α-keto esters, N-tosyl aldimines, acyl chlorides, diol sulphates, disulfides, and diselenides). The corresponding adducts were usually obtained in moderate to good yields and the present method was found to be as good or even better as other most popular approaches. This paper gives an overview of our research efforts in this area as well as results from other groups.     

Reactivity of [Ni(cod)2][Al(ORF)4] towards Small Molecules and Elements

To provide a better understanding of the recently published pure metalorganic Ni^I species, [Ni(cod)₂][Al(OR^F)₄] ( 1 ) [cod = 1,5‐cyclooctadiene, R^F = C(CF₃)₃], further characterizations were performed and analyzed. Thus, the solvation of 1 in THF was examined by EPR, surprisingly disclosing the initiation of a disproportionation reaction to [Ni^II(THF)₆][Al(OR^F)₄]₂ ( 3 ) and Ni⁰. Further studies concerning the ability of 1 to activate small molecules exhibit the formation of a remarkable [Ni₃S₂(cod)₃]²⁺ cluster ( 5 ) in an oxidation reaction with S₈, while EPR measurements of the resulting product in a reaction with oxygen indicate a possible coordination of O₂. Single crystal X‐ray structures as well as spectroscopic analyses of 3 and 5 are described.     

Unexpected reactivity of 2-fluoro-4-(trifluoromethyl)-phenylacetonitrile: isolation and characterization of a trimeric impurity

An uncommon reactivity of 2-fluoro-4-(trifluoromethyl)-phenylacetonitrile, with the loss of three fluorine atoms, is herein reported, the resulting trimeric compound was isolated and characterized by NMR and MS/MS studies. An unprecedented mechanism has been proposed.     

杯[4]芳烃修饰的钌(II)配合物的合成与性质

合成了一种新颖的杯[4]芳烃修饰的钌（Ⅱ）配合物[Ru₂（bpy）₄（H₂L）]（ClO₄）₄（1）（bpy=2,2''-联吡啶,H₂L=11,23-双（2-咪唑[4,5-f]-1,10-菲啰啉）-25,27-二羟基-26,28-二乙酯基丙基-5,17-二-对叔丁基-杯[4]芳烃）,并通过红外光谱、核磁共振氢谱和碳谱、电喷雾质谱和元素分析对该配合物进行了表征。在乙腈/Britton-Robinson缓冲溶液（1∶100,V/V）中研究了配合物1的pH光开关性质。发现随着溶液pH值的变化,配合物1经历两步质子化/去质子化过程,是一个很好的“off-on-off”型pH诱导的分子光开关,其开关比分别为1.42和96.0。通过加入不同阴离子引起配合物1溶液的吸收光谱、发射光谱和核磁共振氢谱的变化研究了其对阴离子的传感性能,发现该配合物可以通过荧光淬灭来识别F^-和OAc^-。另外初步细胞成像实验显示配合物1可以在短时间内穿过细胞膜对细胞质进行染色,而且在成像浓度范围内对Hela细胞体现出低毒性。     

Synthesis of Quaternized poly(4-Vinyl Pyridine) and the Study of its Ion Exchange Property

Lightly cross-linked poly(4-vinyl pyridine) has been synthesized from 4-vinyl pyridine and a small amount of ethylene glycol dimethacrylate (EGDMA) in aqueous medium through micelle technique. The polymer is then quaternized with 1,4-dibromobutane to develop an anion exchange resin with high selectivity and ion exchange capacity at a wide range of pH and temperature. The material exhibits high ion exchange capacity and reverse anion selectivity order compared to commercially available anion exchanger. A method has been designed to separate chromate and sulfate using the synthesized material.     

Mechanism of the interaction of color reagent 1, 3-N, N'-bis-4-(4'-nitro benzenediazo) phenyl squaraine with oxoacid anions

By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-).     

Mechanical properties of molecular composites. I. Poly (p‐phenylene terephthalamide) anion molecules dispersed in poly(4‐vinylpyridine)

Molecular composites have been prepared by dispersing rigid‐rod molecules of ionically‐modified poly(p‐phenylene terephthalamide) (PPTA anion) in a polar poly(4‐vinylpyridine) (PVP) matrix. For concentrations up to 5 wt % of the rigid‐rod reinforcement, the resulting composites are transparent and possess a single glass transition temperature that increases with concentration of the PPTA anion. The mechanical properties of the molecular composites are found to increase with concentration and to attain maximum values at about 5 wt % of the PPTA anion. The enhancement in properties, and the miscibility induced between the two component polymers, is attributed to the development of specific interactions between the ionic groups of the PPTA anion and the polar units of the PVP matrix. When such interactions are not present, as in composites reinforced with non‐ionic PPTA, the samples are opaque and their properties are significantly reduced compared to those of the PPTA anion/PVP composites. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2201–2209, 1999     

介孔TiO_2-SO_4~(2-)的合成及表征

在不使用有机模板剂的条件下,以工业硫酸钛溶液为原料合成了高热稳定的锐钛矿型介孔TiO_2-SO_4~(2-).用X射线衍射、N2吸附、扫描电镜、X射线能谱、傅里叶变换红外光谱和紫外-可见光谱对样品进行了表征,并考察了其光催化性能.结果表明,硫酸根在焙烧过程中与前驱体介孔偏钛酸孔壁上自由羟基的键合起到了孔结构导向及支撑作用,500℃焙烧后样品仍具有202.2m2/g的比表面积及2.8nm的平均孔径.焙烧产物TiO_2-SO_4~(2-)中S=O的强电子诱导效应不仅使邻近的Ti成为超强酸中心,还使二氧化钛的吸收光谱产生30nm的红移,光催化活性显著提高.     

Über die Reaktion von Cp2TiCl2 mit [C(NMe2)3][(CO)4FeC(O)NMe2] – Kristallstruktur von [C(NMe2)3]2[FeCl4]

Concerning the Reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] – Crystal Structure of [C(NMe₂)₃]₂[FeCl₄] The title compound forms by the reaction of Cp₂TiCl₂ with [C(NMe₂)₃][(CO)₄FeC(O)NMe₂] in THF solution. It crystallizes in the space group Pbcn with a = 1 566.6(3); b = 976.4(2); c = 1 580.4(4) pm; Z = 4; R = 3.8%. Each [FeCl₄]^2? in is surrounded by eight cations. Two cations each are connected with one Cl atom by relatively short H …? Cl contacts leading to a distortion of the tetrahedral geometry of the anion.     

Preparation and Crystal Structure of an Acidic Long-chain Polyphosphate: CaH2(PO3)4

Preparation and crystal structure of an acidic polyphosphate of calcium is described. CaH₂(PO₃)₄: monoclinic, P2₁/c, with Z = 2, and a = 5.686(1), b = 9.676(4), c = 8,844(3) Å, β = 92.35(2)°. The crystal structure was solved using 2 321 unique reflections with a final R value of 0.017. The compound is characterized by infinite (PO₃)_n chains running along c and linked together in a three-dimensional way by Ca? O and hydrogen bonds. The two-dimensional linkage of the phosphoric chains by hydrogen bonds is compared to those already observed in ErH(PO₃)₄ and BiH(PO₃)₄.     

Synthesis and Crystal Structure of an Ionic Compound [Fe(CN)_6(phCH_2NC_5H_5)3]·(H_2O)_4

A novel ionic compound [Fe(CN)6(phCH2NC5H5)3]·(H2O)4(Mr = 794.71) has been synthesized and its structure was characterized by IR, elemental analysis and X-ray diffraction. The compound crystallizes in monoclinic, space group P21/c with a = 10.837(2), b = 16.551(3), c = 23.402(5) , β = 97.531(4)o, V = 4161.0(15) A3, Z = 4, Dc = 1.269 g/cm3, F(000) = 1668, μ = 0.414 mm-1, R = 0.0479 and wR = 0.1232. The building unit of the title compound consists of three (phCH2N+C5H5) ions, one [Fe(CN)6]3- anion and four water molecules. According to the structural analysis, [Fe(CN)6]3- are linked together by O–H···N and O–H···O hydrogen bonds, but [Fe(CN)6]3- and [(phCH2N+C5H5)3] ions are bound by electrostatic force to form an ionic compound.     

MoO42-取代对Nasicon型Li3Fe2(PO4)3正极材料电化学性能的影响

以MoO₄^2-部分取代Li₃Fe₂（PO₄）₃中的PO₄^3-,研究表明：加入的MoO₄^2-离子主要以固溶形式存在于Li₃Fe₂（PO₄）₃中,起到了显著改善其电化学性能的作用。其中,MoO₄^2-掺杂浓度为0.3的样品表现出最佳的电化学性能,其在0.5C倍率下的首次放电容量为113.7 mAh·g^-1,这一数值比未掺杂的提高了20.7%;经过60次循环充放电,容量保持率为94%。将放电倍率从0.5C逐步增大至5C,再降至初始的0.5C,并在每个倍率循环10次,这一材料的最终放电容量可达首次0.5C的95%。这些优异的性能应归因于MoO₄^2-掺杂使材料的氧化还原能力增强,氧化还原电对的电势差减小,电池内部的电荷转移电阻减小,以及Li⁺扩散系数增加。     

一类新型四酰胺杯[4]氮杂冠醚的合成及阴离子识别研究

合成了一类新型四酰胺杯[4]氮杂冠醚（4a，4b），其结构经~1H NMR、质谱及 元素分析证实。用紫外可见光谱研究了主体与阴离子之间的相互作用，并计算出其 配合常数。结果表明，四酰胺杯[4]氮杂冠醚（4a，4b）对四面体型阴离子（p - O_2GC_6OPO_3~2_4）没有识别性能，而对平面型阴离子（p - O_2NC_6H_4O）有较 好地选择性识别性能，且主客体间形成1：1配合物。