硫脲类阴离子受体的设计合成与阴离子识别

硫脲类化合物具有生物活性,是优良的氢键供体,与阴离子特别是含氧阴离子形成氢键配合物。本文设计合成了系列二苯基硫脲衍生物,通过取代基效应调控硫脲衍生物分子内电转移过程,阴离子与硫脲基团结合后,增强了分子内供体的给电子能力,进一步促进电荷转移过程,据此识别不同的阴离子。由于主体分子与阴离子间形成氢键的能力及阴离子碱性的差异,可达到选择性结合的目的。     

多足开链化合物与阴离子的相互作用

设计合成了６种萘取代的脲及硫脲类多足开链化合物，利用吸收光谱、荧光光谱及_１Ｈ ＮＭＲ波谱手段详细研究了该类化合物作为主体分子与不同种类的阴离子客体分子间的相互作用．实验表明，客体阴离子Ｈ_２ＰＯ_４~－及ＨＳＯ_４~－可以与三足的脲及硫脲主体分子形成主客体配合物从而诱导主体分子光物理性质发生变化，而且表现出较好的选择性．测定了主客体配合物的稳定常数和化学配位比，对三足脲和硫脲与阴离子客体的选择性和识别作用进行了比较，提出了相应主客体配合物可能的配位方式和结构形式．     

两种含有四硫富瓦烯羧酸基和1,10-菲啰啉配体的金属配合物的合成、结构及光学性质研究

本文用一种水溶性的TTF羧酸盐PropylTTFK2 (1)合成了两种金属配合物,Zn(L1)(Phen)2 (化合物3) 和Cd(L1)(Phen)2?(化合物4) (L1=PropylTTF2-; Phen=1,10-phenanthroline)。用元素分析对二者进行了测试,并解析了二者的晶体结构,具有明显的分子间S???S及H键作用。同时也测定了二者的紫外、荧光和电化学性质,滴定显示两种化合物均是很好的TCNQ电子接受体。     

三丁基锡烃氧(硫)乙酸盐的合成和除草活性测定

本文报道了13种三丁基锡烃氧(硫)乙酸盐的合成及其除草活性的初筛和复筛结果,讨论了化合物的IR和NMR谱,农药活性的测定结果表明,该类化合物的除草活性优于或接近除草剂2,4-D(2,4-二氟苯氧乙酸)。     

含硫脲基的多重氮杂杯[4]芳烃衍生物的合成与有机染料配合性能

以杯[4]芳烃为平台,构筑结构与识别性能独特的杯[4]芳烃衍生物是有机超分子化学的重要研究领域.本文中,杯[4]二芳胺基衍生物3与异硫氰酸苯酯反应得到开链的二硫脲基杯[4]衍生物4,产率为95%.化合物3与等物质的量对二异硫氰酸苯酯反应得到二硫脲基桥连杯[4]衍生物5,产率为80%.与过量的对二异硫氰酸苯酯反应则以产率为82%得到化合物6.化合物6进一步与水杨酰肼反应得到含硫脲基的多重氮杂杯[4]衍生物7,产率为75%.紫外光谱配合实验表明新主体分子4~7对测试的4种有机染料分子(橙黄Ⅰ、茜绿素、维多利亚蓝和亚甲基蓝)均显示出较强的配合能力,配合常数的数量级达10~5,配合比为1∶1.开链结构与多重胺基和芳基结构更有利于配位包合能力的提高.     

前体法制备单分散遥爪聚乙炔

合成了苯基乙烯基亚砜 (PVSO) ,并以萘 碱金属作为引发剂、丁二酸酐作为终止剂 ,进行阴离子聚合 ,制备出单分散、端羧酸盐的苯基乙烯基亚砜的遥爪聚合物 ,聚合物的功能度基本在 1 6 0以上 .在真空加热条件下 ,聚苯基乙烯基亚砜发生侧基热消除反应 ,从而获得末端为羧酸盐的遥爪聚乙炔     

聚羧酸盐在洗衣粉中的应用性能研究

将5种聚羧酸盐和羧甲基纤维素钠（CMC）分别配入洗衣粉中,用卧式去污机做去污实验和20次循环洗涤实验,结果表明：在无磷洗衣粉中加入聚羧酸盐,去污力比加入CMC提高了7．73％～12．20％,灰分沉积比不含聚羧酸盐的降低了49．77％～65．08％,白度保持比不含聚羧酸盐的提高了2．43％～4．02％．在5种聚羧酸盐中,3种不同分子量的聚丙烯酸钠KT-3、PA25CL和445N均可用作无磷洗衣粉的抗再沉积剂,其中KT-3更优．     

凝胶体系中不同结构羧酸盐对草酸钙生物矿化的影响

采用双扩散法研究了凝胶体系中四元羧酸盐(Na2EDTA)、三元羧酸盐柠檬酸钠（Na3cit）、二元羧酸盐酒石酸钠（Na2tart）和一元羧酸盐醋酸钠（NaAc）对草酸钙（CaOx）结晶的影响.抑制一水草酸钙（COM）聚集的能力为:Na2EDTA >Na3cit >Na2tart >NaAc；诱导二水草酸钙（COD）的能力为：Na3cit >Na2tart >Na2EDTA >NaAc.羧酸的抗衡阳离子影响CaOx的结晶. H3cit、Na3cit和K3cit抑制COM聚集和诱导COD形成的能力均为:K3cit-Na3cit >H3cit.无论是诱导COD生成，还是抑制COM聚集，均可以减小结石形成的几率，对临床上防治结石具有积极的意义.     

氯·氨荒酸基·二苯基锗配合物的合成

以二苯基二氯化锡和氨荒酸盐为原料,合成了13种氯．氨荒酸基．二苯基锗配合物,利用元素分析,IR和1HNMR表征了这些配合物的结构,生物活性测试结果表明,该类化合物对KB和Bel癌细胞具有较好的抑制活性。     

氯·杂环羧酸根·二苯基合锗(Ⅳ)的合成及生物活性研究

通过二苯基二氯化锗和杂环羧酸盐以11摩尔比反应,合成了一系列氯@杂环羧酸根@二苯基合锗(Ⅳ),用元素分析、红外光谱、核磁共振氢谱和质谱表征了这些配合物的结构,红外光谱数据表明,配体杂环羧酸根是以单齿形式与锗原子配位.生物活性测试表明,这些配合物显示较强的体外抗癌活性.     

Host-guest complexation of a fluorescent and electrochemical chemsensor for fluoride anion

Host-guest complexation of a ferrocenenylphalene dyad 1, 1,1'-diaceylferrocenyl-3-hydroxyl-2-naphthoylhydrazone, as a fluorescent and electrochemical chemosensor for fluoride anion, was investigated. Crystal structure analysis revealed that the two naphthyl arms of compound 1 positioned in the same side about the ferrocene moiety and interacted through pi-pi stacking interactions. The intermolecular pi-pi stacking interactions and the C-H...pi interactions between the ferrocene moieties and the naphthalene rings linked the molecules together featuring a two-dimensional layered structure. Fluorescence titrations of compound 1 indicated that in the presence of F- and H2PO4-, the emission intensities enhanced significantly. Electrochemical titrations revealed that compound 1 sensed the F- anion in high selectivity with a cathodic shift of 120 mV, and had no sense in recognizing H2PO4- anion. 1H NMR titrations demonstrated that while compound 1 hydrogen-bonded to H2PO4- forming simple 1 : 1 host-guest complex, further addition of F- induced the deprotonation of compound 1.     

Synergistic Spin Transition between Spin Crossover and Spin‐Peierls‐like Singlet Formation in the Halogen‐Bonded Molecular Hybrid System: [Fe(Iqsal)2][Ni(dmit)2]⋅CH3CN⋅H2O

To introduce halogen‐bond interactions between a cation and an anion, a novel Fe^III complex from iodine‐substituted ligands involving a paramagnetic nickel dithiolene anion was prepared and characterized. The compound exhibited the synergy between a spin‐crossover transition and a spin‐Peierls‐like singlet formation. The halogen‐bond interactions between the iodine and the sulfur atoms stabilized the paramagnetic state of π‐spins and played a crucial role in the synergistic magnetic transition between d‐ and π‐spins. In addition, the compound showed the light‐induced excited spin state trapping effect.     

2-(2′-羟基-3′-甲氧基苯基)-5,6-二硝基苯并咪唑的阴离子识别

设计并合成了2-(2′-羟基-3′-甲氧基苯基)-5,6-二硝基苯并咪唑化合物(1),通过X射线单晶衍射研究了该化合物的固态结构.利用紫外-可见光谱技术研究了其对阴离子的识别,发现化合物1能够在DMSO中对AcO-,H2PO4-,OH-的3种离子进行有效识别,同时溶液由原来的黄色变成红色,实现裸眼检测.     

多分支中性受体的合成及αω-二羧酸阴离子识别研究

Two new multi-armed neutral receptors 1 and 2 containing thiourea and amide groups were synthesized by simple steps in good yields. Receptors 1 and 2 have a better selectivity and higher association constants for malonate anion than other anions examined by the present work. In particular, distinct color changes were observed upon addition of dicarboxylate anions to the solution of 1 in DMSO. The UV-Vis and fluorescence spectra data indicate that a 1 ： 2 stoichiometry complex was formed between compound 1 or 2 and dicarboxylate anions of shorter carbon chain, and a 1 ： 1 stoichiometry complex was formed between compound 1 or 2 and dicarboxylate anions of longer carbon chain through hydrogen bonding interactions.     

多钼酸盐[4,4-′H_2bipy]_2 [β-Mo_8O_(26)]的水热合成和晶体结构

利用水热合成方法制备了化合物[4,4′-H2b ipy]2[-βMo8O26],用元素分析、X射线单晶衍射和电子顺磁共振对其结构进行了表征.结构解析表明标题化合物是由β型[Mo8O26]4-多阴离子与质子化的4,4′-联吡啶通过氢键作用形成的三维结构超分子化合物.     

New mixed-anion mercury(II) complex,spectroscopic, thermal and structural studies of [Hg(bipy)2(CH3COO)]2(SO4)·0.5NaCl

A mixed-anion mercury(II) complex of 2,2′-bipyridine (bipy), [Hg(bipy)₂(CH₃COO)]₂(SO₄)?·?0.5NaCl has been synthesized and characterized by elemental analysis, IR-, ¹H NMR- and ¹³C NMR spectroscopy and the structure of this compound determined by single-crystal X-ray diffraction. The thermal stability of this compound was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The complex is a monomer and there are two different Hg atoms with unsymmetrical six-coordinate geometry, formed by four nitrogen atoms of the bipy ligands and two oxygen atoms of the acetate anion. There are short intermolecular C–H?···?O interactions in the packing of this compound.     

An Inclusion Complex of Hexamolybdate inside a Supramolecular Cage and Its Structural Conversion

A self-assembled cage compound consisting of four concave ligands and two square-planar-coordinated Pd(II) ions was found to quantitatively encapsulate a hexamolybdate dianion [Mo(6)O(19)](2-) in solution. The addition of 1 equiv more of [Mo(6)O(19)](2-) to the inclusion complex resulted in the formation of a precipitate from which single crystals were grown. X-ray analysis showed that a structural conversion had taken place upon crystallization: one hexamolybdate anion was found to be wrapped in a chiral, cyclic arrangement of three ligands in the absence of any Pd(II) ions to give a compound of the formula {[Mo(6)O(19)](2-)@(ligand)(3)+2H(+)}. We postulate the stabilization of this arrangement by attractive C-H···O and CF(3)-pyridine interactions.     

[Mo12O40P][C44H38P2][CoC10H10] * 3(C3H7NO): A quasi-ternary intercluster compound

Binary intercluster compounds (IC) can be reduced to basic structure types of ionic solids. We examined the validity of this concept for ternary compounds, on the example of a quasi-ternary intercluster compound made from a Keggin anion ([PMo₁₂O₄₀]^3?), an organic cation (o-xylylenebis(triphenylphosphonium)), and a complex (cobaltocenium). The new compound and its two related quasi-binary IC were investigated by X-ray diffractometry, examined for intermolecular interactions such as hydrogen-bonding, π–, or van der Waals-interactions, and evaluated for possible reductions to basic structure types.     

Noncovalent interactions within a synthetic receptor can reinforce guest binding

Structural and thermodynamic data are presented on the binding properties of anion receptors containing two covalently linked cyclopeptide subunits that bind sulfate and iodide anions with micromolar affinity in aqueous solution. A synchrotron X-ray crystal structure of the sulfate complex of one receptor revealed that the anion is bound between the peptide rings of the biscyclopeptide. Intimate intramolecular contacts between the nonpolar surfaces of the proline rings of the individual receptor moieties in the complex suggest that hydrophobic interactions within the receptor that do not directly involve the guest contribute to complex stability. This finding is supported by a microcalorimetric analysis of the solvent dependence of complex stability, which showed that increasing the water content of the solvent has only a weak influence on the Gibbs energy of binding. Hence, the increasing amount of energy required for desolvating the binding partners in solutions containing more water is almost compensated by the increasingly favorable hydrophobic interactions. Further observations that suggest that guest-induced intra-receptor interactions contribute to guest binding are (i) anion binding of a monomeric cyclopeptide lacking the covalent linkage between the two rings leads to the formation of 2:1 complexes; (ii) in the crystal structure of the 2:1 iodide complex of this monotopic receptor, a similar arrangement of the two cyclopeptide rings has been found as in the sulfate complex of the biscyclopeptide; (iii) complex formation of the monomeric cyclopeptide in aqueous solution is highly cooperative with a large stability constant corresponding to the formation of the 2:1 complexes from relatively instable 1:1 complexes; (iv) the monomeric cyclopeptide forms only 1:1 anion complexes in DMSO where hydrophobic interactions do not take place; and (v) introducing polar hydroxy groups on the proline rings of the monomeric cyclopeptide disrupts cooperativity causing the formation of only 1:1 complexes even in aqueous solution. Taken together these observations demonstrate that, in addition to direct receptor-substrate interactions, noncovalent interactions between the two subunits of such biscyclopeptides contribute significantly to anion complex stability. Reinforcement of molecular recognition through intra-receptor interactions should be an attractive new strategy to boost host-guest affinities.     

Synthesis,Structure, and Supramolecular Chemistry of Three Azide Manganese Complexes with 2, 6‐Bis(benzimidazol‐2‐yl)pyridine

Three azide complexes with the tridentate ligand 2, 6‐bis(benzimidazol‐2‐yl)pyridine (H₂BBIP) were synthesized and their complicated supramolecular interactions were investigated with single‐crystal X‐ray diffraction. Interestingly, the complexes are assembled by bifurcated hydrogen bonding, double helical π–π stacking, or anion–π stacking interactions of the benzimidazole rings by tuning the reaction conditions (temperature, ratio, solvent). Complex 1 is a mononuclear compound, namely, Mn(H₂BBIP)N₃(CH₃O) · CH₃OH. In its 3D supramolecular network, the nitrogen atom of the azide anion is acting as hydrogen bonding bifurcated acceptor. Complex 2 is a dinuclear compound, namely, Mn₂(H₂BBIP)₂(N₃)₂ · (H₂O)_0.5. The dinuclear unit is connected by intramolecular π–π stacking interactions. Furthermore, double helical π–π stacking interactions in the benzimidazole rings are observed. Complex 3 , Mn₂(H₂BBIP)₂(N₃)₂ · CH₃OH, can be formulated as a pseudopolymorph of complex 2 , which exhibits intramolecular π–π stacking interactions as well as anion–π interactions in the dinuclear unit.