F Cl_2→ClF Cl和Cl′F Cl→Cl′ ClF的反应机理

用密度泛函理论(DFT)B3LYP方法,取6-311G基组,计算研究了F＋Cl2→ClF＋Cl的反应机理.求得1个线形和2个三角形过渡态,反应能垒分别为1.24、46.37和105.09kJ·mol－1;同时发现F以∠FClCl为10～20°（或120～160°）进攻Cl2时,反应无能垒.此外,求得对称反应Cl′F＋Cl→Cl′＋ClF的能垒为40.57kJ·mol－1的1个过渡态.     

离子色谱仪和自动快速燃烧炉联用测定卤素时内标物选择

探讨了当离子色谱仪和自动快速燃烧炉联用测定卤素时内标物的选择问题。试验表明:当卤素系列标准溶液和吸收液都采用碳酸钠-碳酸氢钠缓冲溶液作为介质时,以C_2O_4~(2-)作为内标物,既能保持卤素离子(F~-、Cl~-、Br~-、I~-)有良好的分离度,又能保持长久的稳定性,同时还可以避免样品本身以及外界的干扰,是该试验中比较理想的内标物。     

Investigation of Intermolecular C-H···Halogen Hydrogen Bonded Supramolecular Assemblies in Three Copper(Ⅰ) Complexes Formed by 3,3'-Dimethoxy-6,6'-dimethyl-2,2'-bipyridine Ligand

Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic Pbca,a = 18.5858(12),b = 8.1821(5),c = 20.6066(13) ,V = 3133.7(3) 3,Z = 8,Dc = 1.843 g/cm3,F(000) = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2:Orthorhombic Pbca,a = 18.7883(16),b = 8.3249(7),c = 19.0294(17) ,V = 2976.4(4) 3,Z = 8,Dc = 1.731 g/cm3,F(000) = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3:monoclinic P21/c,a = 13.812(10),b = 9.910(7),c = 23.444(17) ,β = 104.3350(10)°,V = 3090(4) 3,Z = 4,Dc = 1.476 g/cm3,F(000) = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2(1) and C14H16BrCuN2O2(2) are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional(3D) supramolecular network in 1 and a two-dimensional(2D) sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4(3) is ionic.In 3,the [Cu(dmbp)2]+ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional(1D) chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated.     

笼形聚偕胺肟树脂的研究─—卤素及其化合物在树脂上的吸附

考查了碱处理笼形聚偕胺肟树脂（BCAO）和乙酸、硝酸或盐酸处理的笼形聚偕胺肟树脂（HOAC／ACAO、HNO。／ACAO、HCI／ACAO）对卤化物、卤酸盐和卤素的吸附行为。发现BCAO和HOAC／ACAO不吸附卤化物和卤酸盐；HNO3/ACAO和HCl/ACAO对两类化合物则表现出不同的吸附能力。BCAO和ACAO均吸附溴和碘，并符合Freundlich和Langmuir等温吸附方程。研究了溴在BCAO上的吸附动力学，讨论了吸附机理。     

卤素掺杂PMP低密度泡沫材料的研制

在ICF实验研究中，聚4-甲基-1-戊烯（PMP）因只包含C、H两种元素，且泡沫容易加工成型，因而在ICF物理实验中得到了广泛的应用。近年来随着强激光技术的发展，在实验室中利用激光与黑腔靶耦合产生的辐射场开展辐射输运实验研究已成为可能。在辐射输运过程中，输运介质的性质影响着辐射传输的过程。若在腔内泡沫材料中掺入一定量的中、高原子序数亿l介质可以在输运介质热容量变化不大的同时大为降低泡沫中的Rosseland平均自由程，从而提高其辐射传输光学厚度。因此，进行掺杂聚合物低密度泡沫材料的研制具有重要的意义。本年度主要开展了卤素掺杂PMP低密度泡沫材料的研制工作，六氯苯和六溴苯具备溶剂（均四甲苯／萘）的良好相溶性及较高的卤素原子含量，以六氯苯和六溴苯为掺杂单体，PMP为泡沫骨架材料，利用热诱导倒相法制备出最大质量分数为58．91％的卤素掺杂低密度泡沫材料。     

明胶与AgBr晶体颗粒相互作用的研究

为了探讨明胶在照相乳剂中的行为 ,用红外光谱法研究了明胶与AgBr晶粒间的相互作用 ,证实了明胶 AgX照相乳剂的晶粒吸附有明胶 .红外光谱分析结果表明 ,明胶与AgBr晶粒间的作用除了明胶与Ag+ 的化学亲和力外 ,明胶与Br- 之间还存在静电作用 .而且 ,明胶的疏水侧链与AgBr晶粒疏水区之间还存在另一种作用力 ,该作用力可能是范德华力 ,它对乳剂红外光谱的影响显示在 10 0 0～ 12 0 0cm- 1.由于用鱼胶和骨胶制作的乳剂在AgBr的晶体形态和乳剂的感光性能方面都显示出明显的差异 ,因此 ,还比较了这两种明胶与AgBr的作用特性     

Ab Initio Calculations on Halogen Bond Between N——Br and Electron-donating Groups

Ab initio calculations of complexes formed between N-bromosuccinimide and a series of electron-donating groups were performed at the level of MP2/Lanl2DZ to gain a deeper insight into the nature of the N—Br halogen bonding. For the small complexes, H3C—Br…NH3 and H2N—Br…NH3, the primary calculation has demonstrated that the N—Br in H2N—Br…NH3 can form a much stronger halogen-bonding complex than the C—Br. A comparison of neutral hydrogen bond complex series reveals that the electron-donating capacities of the atoms decrease in the order, N>O>S; O(sp3)>O(sp2), which is adequate for the C—Br halogen bonding. Interaction energies, in conjunction with the geometrical parameters show that the affinitive capacity of trihalide anions X-3 with N-bromosuccinimide are markedly lower than that of the corresponding X- with N-bromosuccinimide, even lower than those of neutral molecules with N-bromosuccinimide. AIM analyses further confirmed the above results.     

氧弹燃烧–离子色谱法测定电子电气产品中卤素

利用氧弹燃烧处理样品,采用离子色谱法测定电子电气产品中的卤素含量。在0.2~1.0 mg/L范围内,氟、氯、溴、碘离子的质量浓度与离子色谱峰面积呈良好的线性关系,线性相关系数均大于0.999,各离子加标回收率为90%~110%,测定结果的相对标准偏差不超过5.0%(n=6)。该方法快速、准确,可应用于电子电气产品中卤素的测定。     

A pillar[5]arene-based side-chain pseudorotaxanes and polypseudorotaxanes as novel fluorescent sensors for the selective detection of halogen ions

A pseudorotaxane and its polypseudorotaxanes formed between pillar[5]arene moieties and noctylpyrazinium cations as novel fluorescent sensors for the selective detection of halogen ions were reported.A collapse of these pillar[5]arene-based pseudorotaxanes and polypseudorotaxanes occurred upon the addition of Cl,Br,and I（tetrabutylammonium salts）,respectively,leading to their fluorescence recovery.The fluorescence enhancement of the pseudorotaxane and the polypseudorotaxanes increases in the order of I