香豆素酰胺类化合物的合成及光谱特性

用(取代)香豆素-3-甲酰氯(Ⅰa～Ⅰc)和取代2-氨基苯并噻唑(Ⅱa～Ⅱd)作用合成了12种新的目标化合物(Ⅲa～Ⅲl),用HRMS、IR、1H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析。研究发现:在紫外光谱中,新化合物(Ⅲa～Ⅲl)和原料化合物(Ⅰa～Ⅰc)相比,因共轭链的增长而使其最大吸收波长(λmax)红移;12种化合物表现出比原料化合物(Ⅰa～Ⅰc)较强的荧光性能。     

N-(取代)-1,3,4-噻二唑基香豆素酰胺类化合物的合成及光谱特性

用6-氯香豆素-3-甲酰氯(Ⅰ)和5-(取代)-2-氨基-1,3,4-噻二唑(Ⅱa-Ⅱi)作用合成了9种新的目标化合物(Ⅲa-Ⅲi),用HRMS,IR和1 H NMR对化合物结构进行了表征,确定了化合物的结构,并对其紫外吸收光谱和荧光光谱进行了分析.研究发现:在紫外光谱中,新化合物(Ⅲa-Ⅲi)和2种原料化合物相比,因共轭链的增长而使其最大吸收波长(λmax)红移;9种化合物表现出比原料化合物(Ⅰ)较强的荧光性能.     

两个基于MnⅢ席夫碱氰基桥联化合物的合成、结构和磁性

本文利用MnⅢ席夫碱配合物作为前驱体,与含有氰根桥联配体的构筑基块K3[CoⅢ(CN)6]或Na[N(CN)2]反应合成了2个新的化合物[MnⅢ6(Salen)6(H2O)6.CoⅢ(CN)6][CoⅢ(CN)6].6H2O(1)和[MnⅢ(5-Br)Salen.N(CN)2].H2O(2),其中Salen为二-邻苯甲醛乙二胺。利用红外光谱、元素分析和X-射线单晶衍射分析对其结构进行了表征并测试了其磁学性质。结构分析表明化合物1由1个七核阳离子簇[Mn6Co]3+和一个平衡阴离子[Co(CN)6]3-组成的离子对化合物。而化合物2则为由MnⅢ组成的一维中性链结构,[N(CN)2]-利用叠氮桥联方式和金属离子配位。磁性研究表明,化合物1中[Co(CN)6]3-几乎不传递磁耦合作用,所以是一个顺磁体,但MnⅢ自身的零场分裂导致低χMT在低温时随温度下降而减小,而2则表现出弱的链内反铁磁性耦合作用。对比化合物1和2的磁性得知共轭体系[N(CN)2]-比同样是五原子配体[Co(CN)6]3-传递较强磁耦合作用。     

分化诱导剂的合成及晶体结构

合成出四个分化诱导剂,N,N,N',N'-四乙酰已二胺(Ⅰ),1,6-二烟酰已二胺(Ⅱ),1,6-二(3,5-二氧哌嗪)已烷(Ⅲ)和1,6-二[3,3'-(5,5-二甲乙内酰脲)]已烷(Ⅳ),对合成方法和路线进行了优化,通过元素分析、质谱、核磁和红外进行了表征,测定了化合物Ⅲ对人白血病细胞的分化诱导活性,利用单晶X射线四圆衍射测定了化合物Ⅳ的晶体结构,并与化合物Ⅰ,Ⅱ,Ⅲ的晶体结构进行了比较。     

皱叶香茶菜化学成分的研究

从采自西藏的皱叶香茶菜中分离鉴定了3对B-闭联对映贝壳杉烯型二萜化合物:二萜化合物皱叶香茶菜素(Ⅰ)和二氢皱叶香茶菜素(Ⅱ);isodocarpin(Ⅲ)和dihydroisodocarpin(Ⅳ)及Carpalasionin(Ⅴ)和dihydrocarpalasionin(Ⅵ)。(Ⅰ)、(Ⅲ)和(Ⅴ)分别与对应的二氢化合物(Ⅱ)、(Ⅳ)和(Ⅵ)以混合物的形式被分离和鉴定。化合物(Ⅱ)为新化合物,(Ⅰ)、(Ⅳ)和(Ⅵ)首次在自然界发现,(Ⅲ)和(Ⅴ)为已知化合物。     

两种四足席夫碱对环境水样中Fe(Ⅲ)离子的比色识别（英文）

使用季戊四胺与水杨醛、邻香兰素缩合反应得到了两种席夫碱化合物1和2。化合物1和2均可用于不同水样Fe(Ⅱ)和Fe(Ⅲ)离子的比色识别。通过光谱滴定及液质谱联用等方法研究了化合物1和2与Fe(Ⅲ)的识别作用,化合物1和2与Fe(Ⅲ)离子的配位比为1∶1,对Fe(Ⅲ)铁离子的检出限分别为0.19和0.21μmol·L~(-1),低于世界卫生组织饮用水检出标准(5μmol·L~(-1)),具有一定的实用价值。     

氢键桥连一维铁(Ⅲ)自旋交叉化合物的合成和性质（英文）

合成了一例单核铁(Ⅲ)化合物[Fe~Ⅲ(Him)_2(4-Me Ohapen)](CH_3SO_3)(1,Him=imidazole,H_2(4-Me Ohapen)=N,N′-bis(4-methoxy-2-hydroxyacetophenylidene)ethylenediamine),并对其晶体结构与磁性质进行了表征。单晶X射线分析表明,该化合物中的磺酸根阴离子通过氢键桥连[Fe~Ⅲ(Him)_2(4-Me Ohapen)]~+阳离子,并以此形成了一维链状结构。磁化率测试表明,该化合物具有突变型自旋交叉行为,其转变温度为T_(1/2)↓=163 K及T_(1/2)↑=167 K。这些研究结果表明,阴阳离子之间的氢键对改进自旋交叉化合物的性质具有重要作用。     

气相色谱法研究配位化合物的热稳定性ⅩⅩ.草酸铁(Ⅲ)-硝酸钠在氢气中的固相氧化还原反应

以气相色谱为主要手段,配合Mossbauer波谱、X射线衍射等方法研究了草酸铁(Ⅲ)与硝酸钠在氢气氛中的固相反应,实验结果表明:240℃前两者不发生反应,草酸铁(Ⅲ)还原分解;260—320℃固相间发生强烈氧化还原反应,大量二氧化碳放出,并伴有少量氧和一氧化氮,380℃后,生成的亚硝酸钠与未反应的硝酸钠在铁(Ⅲ)化合物作用下,提前分解,同时铁(Ⅲ)化合物转化成γ-Fe_2O_3.     

Rh(Ⅲ)催化2-苯基吡啶溴代反应:可能的Rh(Ⅴ)中间体的选择性消除

Rh_2(TFA)_4与2-苯基吡啶发生C-H活化得到的铑(Ⅲ)二吡啶化合物被NBS氧化后在25oC条件下发生C-C键形成的还原消除过程得到Rh(Ⅲ)金属化合物。而在100℃条件下发生C-Br键形成的还原消除过程得到二溴代苯基吡啶化合物,并实现了催化反应。反应可能是经历高价Rh(Ⅴ)中间体过程,在不同温度下选择性发生C-C键或者C-Br键形成消除反应。     

稀土碘氧化物的制备和X-射线分析

用改进的助熔剂法制备了十五个稀土元素(Ⅲ)的碘氧化物。通过化学和X光衍射分析方法确定这些化合物组成为LnOI,并计算了它们的晶胞参数。对Eu(Ⅲ)的碘氧化物异常现象进行了讨论。     

金属锰Corrole的脱金属研究

合成了中位带有不同取代基的锰corrole配合物1-Mn, 2-Mn, 3-Mn, 4-Mn,并研究了其酸解和还原脱金属特性。结果表明取代基的性质对脱金属产率有很大的影响。缺电子金属锰corrole的酸解脱金属产率比富电子金属锰corrole高,而还原脱金属产率的顺序则正好相反。     

Characterization and Crystal Structure of a New Holmium(Ⅲ) Complex with the Macrocyclic Ligand Derived from 2,6-Dfformyl-4-methylphenol and Diethylenetriamine

The title compound (13,27-dimethyl-3,6,9,17,20,23-hexaazatricyclo-[23.3.1.111,15]-triaconta- 1 (29),2,9,11,13,15(30), 16,23,25,27-decaene-29,30-diol-N3,N6,N9,O29,O30)-bis(nitrato-O,O')-holmium(Ⅲ) nitrate hydrate has been prepared and characterized by elemental analysis, infrared spectra, and electrospray mass spectra. Its crystal and molecular structures were determined by X-ray diffraction methods. The crystal crystallizes in the monoclinic system, space group C2/c with a = 23.737(12), b = 14.237(7), c = 19.801(10) (A), β = 91.36(1)°, Mr = 831.57, V = 6690(6) (A)3, Z = 8,Dc = 1.651 g/cma, F(000) = 3344, R = 0.0482 and wR = 0.0923. The holmium ion is located in one of the compartments of the macrocyclic ligand and presents a distorted tricapped trigonal prismatic coordination geometry. The macrocycle is coordinated with two oxygen and three nitrogen atoms.Two nitrates are chelated in the opposite positions of the macrocycle, and the third one is ionic.     

Phenylacetylene macrocycles with two opposing bipyridine donor sites: syntheses, X-ray structure determinations, and Ru complexation

Reaction of the known macrocycle 1a, which contains two bipyridine units in opposing sides, with two equivalents of [Ru(bipy)2Cl2] furnishes the doubly exocyclically complexed macrocycle 8a in 55% yield. Synthesis of the shape-persistent macrocycle 1c by Hagihara-Sonogashira cross-coupling chemistry of suitably functionalized building blocks is reported. This macrocycle was also converted into a Ru complex (8c). X-ray analysis of single crystals of 1b and 1c shows a layered structure that contains "channels" filled with solvent molecules and parts of the flexible chains, with which the cycle is decorated for solubility reasons.     

Threading-followed-by-shrinking protocol for the synthesis of a [2]rotaxane incorporating a Pd(II)-salophen moiety

This communication describes a new protocol for the construction of [2]rotaxanes: "threading-followed-by-shrinking". This approach involves the threading of a rodlike unit through a crown ether-like macrocycle and then shrinking the size of the macrocycle's cavity through coordination of a transition-metal ion by a salophen moiety in the macrocycle. The self-assembly of the macrocycle and a thread, followed by addition of palladium acetate, afforded the [2]rotaxane, which contains a palladium(II)-salophen moiety, after counterion exchange. This [2]rotaxane was characterized fully by NMR and IR spectroscopic, mass spectrometric, and elemental and X-ray crystallographic analyses.     

Extra large macrocycle: 40-membered macrocycle via 2:2 cyclization and its dimercury(II) complex

A large 40-membered N(4)O(4)S(4) macrocycle (L(2)) was obtained through a 2:2 cyclization of the corresponding dithiol and dichloride as a minor product during the preparation of a 20-membered N(2)O(2)S(2) macrocycle (L(1), 1:1 cyclization product). Each macrocycle was successfully separated from the mixed products and identified. The larger macrocycle L(2) allowed the preparation of its dimercury(II) complex, adopting a one-dimensional (1D) stairway-like polymeric chain linked with the anion. A monomercury(II) complex of the smaller macrocycle L(1) was also prepared. Both complexes and the larger macrocycle L(2) were structurally characterized by the single crystal X-ray analysis.     

Fluorescent Alteration on a Bistable Molecular Shuttle

Solvent driven molecular shuttles containing a pyrene‐connected macrocycle and an intramolecular charge‐transfer (ICT) chromophore stopper are constructed. In one of the molecular shuttles, a long C‐10 chain is introduced in the thread to separate the peptide station and the ICT stopper. The macrocycle stays in the peptide station in apolar solvents and moves to the C10‐chain station in highly polar solvents. This moving process alters the electronic interaction between the pyrene unit in the macrocycle and the ICT stopper, which induces the change of the pyrene fluorescence emission. The molecular shuttle exhibits stronger emission when the macrocycle is adjacent to the ICT stopper.     

Optically probing molecular shuttling motion of [2]rotaxane by a conformation-adaptive fluorophore

A bistable [2]rotaxane with a conformation-adaptive macrocycle bearing a 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) unit was synthesized, which could be utilized to optical probe the molecular shuttling motion of the functionalized rotaxane system. The UV–vis, ¹H NMR and PL spectroscopic data clearly demonstrated that the DPAC ring was interlocked onto the thread and the fluorescence intensity of the DPAC unit in the macrocycle was effectively regulated by the location change of the macrocycle along the thread under acid/base stimulation, which was attributed to the modulation of the intramolecular photo-induced electron transfer between the DPAC unit and the methyltriazole (MTA) unit. This bistable rotaxane system containing a conformation-adaptive fluorophore unit in the macrocycle moiety opens an alternative way to design functional bistable mechanically interlocked molecules.     

Cooperative self-assembly of a macrocyclic Schiff base complex

A metal template approach affords in high yield a tetra-Zn(salphen) macrocycle (3) which shows strong and cooperative self-assembly mediated by the formation of Zn(salphen) dimer units held together via μ(2)-phenoxo interactions. A cooperative binding mode for the tetranuclear Zn(4) macrocycle 3 is supported by comparison of UV-vis and fluorescence titration data recorded for 3 when compared with respective mononuclear and dinuclear Zn(salphen) model compounds. UV-vis dilution experiments carried out for Zn(4) macrocycle 3 and its Pd(4) analogue 4, as well as comparative TEM studies involving the same tetranuclear macrocycles further support the strong assembly behavior of 3. This self-assembly seems to be primarily dictated by its ability to form multiple, self-assembled dimeric [Zn(salphen)](2) units.     

Rigid macrocyclic triamides as anion receptors: anion-dependent binding stoichiometries and 1H chemical shift changes

The cyclic triamide of 3'-amino-3-biphenylcarboxlic acid is readily synthesized in a stepwise manner and represents a novel class of anion receptors with a large central cavity. This macrocycle binds more strongly to tetrahedral anions than spherical or planar anions in organic solvents. The binding stoichiometries for anions with symmetrical charge distribution depend on the solvent polarity, while tetrahedral p-tosylate binds to the macrocycle with 1:1 stoichiometry in all solvents studied. The (1)H NMR chemical shift changes of the protons lining the interior of the macrocycle's central cavity also depend on the geometry of the bound anion. The importance of the convergent array of hydrogen bond donors for anion binding by the macrocycle was confirmed by control studies with an acyclic triamide and a macrocycle with intramolecular hydrogen bonds.     

A molecular shuttle for driving a multilevel fluorescence switch

A [2]rotaxane-based molecular shuttle comprised a macrocycle mechanically interlocked to a chemical "dumbbell" has been prepared in high yields by a thermodynamically controlled, template-induced clipping procedure. This molecular shuttle has two different recognition sites, namely, -NH2 +- and amide, separated by a phenyl unit. The macrocycle exhibits high selectivity for the -NH2+- recognition sites in the protonated form through noncovalent interactions, which include 1) N+-H...O hydrogen bonds; 2) C-H...O interactions between the CH2NH2+CH2 protons on the thread and the oligo(ethylene glycol) unit in the macrocycle; 3) pi...pi stacking interaction between macrocycle and aromatic unit. Upon deprotonation of the [2]rotaxane the macrocycle glides to the amide recognition site due to the hydrogen bonds between the -CONH- group and the oligo(ethylene glycol) unit in the macrocycle. The deprotonation process requires about 10 equivalents of base (iPr2NEt) in polar acetone, while the amount of base is only 1.2 equivalents in apolar tetrachloroethane. Upon addition of Li+, the conformation of the [2]rotaxane was altered as a result of the collective interactions of 1) hydrogen bonds between pyridine nitrogen and amide hydrogen atoms; 2) coordination between the oligo(ethylene glycol) unit, amide oxygen atom and Li+ cation. Then, when Zn2+ ions are added, the macrocycle returns to the deprotonated -NH- recognition site owing to coordination of the macrocycle and -NH- from the axle with the Zn2+ ion. All the above-mentioned movement processes are reversible through the alternate addition of TFA/iPr2NEt, Li/[12]-crown-4 and Zn2+/ethylenediaminetetraacetate (EDTA), by virtue of hydrogen bonding and metal-ion complexation. Significantly, the three independent movement processes are all accompanied by fluorescent responses: 1) complete repression in the protonated form; 2) low-level expression in the deprotonated form; 3) medium-level expression following addition of Li+; 4) high-level expression on complexation with Zn2+.