两种臂式荧光氮杂冠醚化学传感器

合成了萘基臂式苯并氮杂15-冠-5 (3)和5-氯喹啉基臂式苯并氮杂15-冠-5 (4)两种荧光化学传感器, 由元素分析、NMR等进行了结构表征|在乙醇溶剂中采用紫外光谱和荧光光谱法分别研究了冠醚3和4对金属离子K^＋, Ca^2＋, Mg^2＋, Pb^2＋, Co^2＋, Ni^2＋, Mn^2＋, Cu^2＋, Zn^2＋, Cd^2＋和Hg^2＋的选择性传感性能. 结果表明, 冠醚3仅对Cu^2＋离子有显著的传感作用, 是一种典型的辐射能量转移过程. 冠醚4对Ni^2＋, Co^2＋, Cu^2＋和Mn^2＋离子有特殊的敏感性, 金属离子浓度逐渐增大使冠醚4产生先增强后猝灭的荧光现象, 荧光增强归因于阻断了从冠环氮原子到喹啉荧光体的弱光诱导电子转移(PET)过程, 而选择性猝灭源于冠醚环与喹啉基团对金属离子协同螯合的机制. 冠醚3和4的构性关系表明, 发光体基团对传感器的选择性能够产生重要的影响.     

芳香桥式双(苯并氮杂-15-冠-5)的合成及其对碱金属和重金属离子的选择键合

通过11,12-苯并-1,7,10,13-四氧杂-4-氮杂环十五烷-11-烯(苯并氮杂-15-冠-5)分别与间二苄溴, 间苯二甲酰氯和对苯二甲酰氯反应, 合成了N,N'-间二苄基双(苯并氮杂-15-冠-5) (1)、N,N'-间苯二甲酰基双(苯并氮杂-15-冠-5) (2)和N, N'-对苯二甲酰基双(苯并氮杂-15-冠-5) (3) 等三个芳香桥式双(苯并氮杂-15-冠-5)衍生物, 并解析了化合物3的晶体结构. 进而采用溶剂萃取的方法研究了它们与一价金属阳离子的键合行为. 结果表明, 双冠醚2对碱金属钠离子和重金属铊离子表现出较高的选择萃取能力, 而双冠醚1对重金属银离子表现出较高的选择萃取能力.     

新型四酰胺杯[4]氮杂冠醚的合成及对阴离子的光化学传感性质研究

合成了一类新型四酰胺杯[4]氮杂冠醚(5a, 5b), 用紫外和荧光光谱研究了主体与阴离子客体之间的识别性能. 主体分子5a或5b加入到对硝基酚氧阴离子的CHCl₃溶液中, 主客体间形成超分子复合物使得客体阴离子423 nm处吸光度降低且溶液从黄色变为无色. 受体5a, 5b与p-NO₂C₆H₄O^－, F^－, 相互作用, 荧光光谱发生变化, 并且对于p-NO₂C₆H₄O^－具有较好的选择性识别能力, 其荧光光谱强度改变强弱的顺序为p-NO₂C₆H₄O^－＞F^－＞H₂PO₄^－>>Cl^－, Br^－, I^－. 荧光光谱滴定的结果经非线性拟合, 结果表明主客体间形成1∶1络合物.     

以2-苯氧乙基为氮支链的[18]和[15]环系氮支套索冠醚的合成及其络合性能

以2-苯氧乙醇为起始剂, 合成了两种新型氮支套索冠醚: N-(2-苯氧乙基)单氮杂-18-冠-6 (18CE)与N-(2-苯氧乙基)单氮杂-15-冠-5 (15CE). 通过红外光谱、核磁共振氢谱和紫外光谱表征了新冠醚及其中间体的结构. 用电导滴定法研究了两冠醚与Na^＋, K^＋, Ag^＋, NH^4＋, Ni^2＋, Cu^2＋, Pb^2＋和Co^2＋在25 ℃的配位作用, 计算了1∶1配合物的稳定常数. 实验结果表明, 由于N-(2-苯氧乙基)引入氮杂冠醚环和参与配位, 18CE和15CE配合物的稳定常数分别比单氮杂-18-冠-6, N-(2-羟基乙基)单氮杂-18-冠-6, N-(2-甲氧基乙基)单氮杂-18-冠-6和单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5, N-(2-甲氧乙基)单氮杂-15-冠-5的对应配合物明显提高. 配合物的稳定常数和紫外光谱皆提供了支链的苯氧基参与配位的信息.     

四氮杂-18-冠-6的锌/铜(Ⅱ)配合物的合成与结构

合成了1,10-二氧-4,7,13,16-四氮杂-18-C-6(以下用L代表)的硝酸锌和硝酸铜(Ⅱ)配合物.配合物Cu(L)(NO3)₂晶体属正交晶系,Pbca空间群,晶胞参数如下:a=1.5744(6)nm,b=1.2676(4)nm,c=1.8983(6)nm,V=3.789(2)nm³,Z=8,最终偏离因子R₁=0.0431,wR₂=0.0904.配合物Zn(L)(NO₃)₂晶体属正交晶系,Pnna空间群,晶胞参数a=1.61356(10)nm,b=1.32871(11)nm,c=0.86260(5)nm,V=1.8494(2)nm³,Z=4,最终偏离因子R₁=0.0718,wR₂=0.1950.冠醚环上的4个氮原子和2个氧原子都参与了配位,NO₃^-未参与配位,中心金属离子的配位数为6.红外光谱、¹H NMR和EPR谱等研究佐证了上述测定结果.Cu(L)(NO₃)₂循环伏安实验表明该配合物在-1.0～0V电压范围内,只发生Cu(Ⅱ)→Cu(Ⅰ)的还原反应,而在-1.6～0V电压范围内,发生Cu(Ⅰ)→Cu(0)的反应.     

含松香骨架的手性氮杂冠醚的合成及其在不对称Michael 加成反应中的应用

以松香为原料, 合成了4个手性氮杂冠醚: N-脱氢松香基单氮杂-12-冠-4、N-脱氢松香基单氮杂-15-冠-5、N-脱氢松香基单氮杂-18-冠-6和N-降解脱氢松香基单氮杂-12-冠-4, 并用于催化不对称查尔酮Michael加成反应, 发现这些手性氮杂冠醚可以有效地催化2-硝基丙烷与查尔酮的不对称Michael加成, Michael加成产物ee最高达35%.     

18-冠-6修饰苝酰亚胺衍生物的合成及离子识别行为

合成了一种18-冠-6修饰的苝酰亚胺衍生物(1), 研究了其作为主体对金属离子与阴离子的选择性识别行为. 结果表明, 主体1对Ba²⁺离子具有一定的选择性响应, 并可以通过Ba²⁺调控主体1的堆积行为; 主体1还对F^-离子有选择性响应, F^-与苝酰亚胺单元之间发生了阴离子-π相互作用.     

N-(2-对甲苯磺酰胺基乙基)单氮杂冠醚的合成及其晶体结构

N-对甲苯磺酰基乙二胺分别与1,11-二碘-3,6,9-三氧杂十一烷和1,14-二碘-3,6,9,12-四氧杂十四烷反应,制得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4或15-冠-5;当用N-(2-对甲苯磺酰胺基乙基)二乙醇胺与1,11-二对甲苯磺酸酯-3,6,9-三氧杂十一烷反应时,才能获得N-(2-对甲苯磺酰胺基乙基)单氮杂-18-冠-6.从甲醇溶液中培养得N-(2-对甲苯磺酰胺基乙基)单氮杂-12-冠-4单晶,属单斜晶系,P2₁/a空间群;a=1.4229(1)nm,b=0.9595(2)nm,c=1.4564(1)nm,β=102.20(1)°,V=1.9435nm³,Z=4.最终偏离因子R=0.043.     

调控发光波长: 新型2-取代8-羟基喹啉衍生物金属锌配合物的合成与特性研究

设计合成了2-[(2'-芴基)-乙烯基]-8-羟基喹啉(6)、2-[(2'-菲基)-乙烯基]-8-羟基喹啉(7)及其金属锌配合物8和9; 用UV-Vis, FT-IR, ESI-MS, ¹H NMR和元素分析确认了化合物6和7的结构; 并用四甲基偶氮唑盐微量酶反应比色法(MTT法)研究了其调控骨髓间质干细胞增殖的作用, 结果表明, 化合物6和7对干细胞有明显的增殖作用. 用FT-IR, FAB-MS和元素分析表征了金属锌配合物结构, 光致发光光谱测试结果表明, 化合物8的发光峰值为602 nm, 发黄光; 化合物9的发光峰值为628 nm, 发橙红色光.     

二苯并-18-冠-6-铵与硫氰酸钴配合物的晶体和分子结构

冠醚化合物因具有环状空腔结构的特点而有独特的配位性能.随着冠醚环上杂原子的数目、种类不同(如氧、氮、硫、磷)而有不同的配合能力及其配位本质.除此之外,冠醚环上电子密度分布对配位能力具有重要作用;金属离子的电子结构对配位性质也有很大影响.对于不是很大的冠醚环来说,通常只配位碱金属、碱土金属、镧系、锕系元素,而较难配位过渡金属离子.近年来,有人通过在冠醚环上引进吸电子基团,减低环上氧原子的电子给予体性质,以求改变配位性能.我们感兴趣的是在以普通冠醚为配体时,配合物同时包含有碱金属与过渡金属离子的配位情况与结构.作者曾对18-冠-6在有钾离子与钴离子体系中的配位情况与晶体结构作了报道,本文研究了硫氰酸铵及氯化钴与二苯并-18-冠-6反应生成的配合物结构及其特点.     

Complexation of Ba2+, Pb2+, Cd2+, and UO22+ Ions with 18-Crown-6 and Dicyclohexyl-18-Crown-6 in Nitromethane and Acetonitrile Solutions by a Competitive NMR Technique Using the 7Li Nucleus as a Probe

[⁷Li] NMR measurements were used to determine the stoichiometry and stability of Li⁺ complexes with 18-crown-6 and dicyclohexyl-18-crown-6 in nitromethane and acetonitrile solutions. A competitive [⁷Li] NMR technique was also employed to probe the complexation of Ba²⁺, Pb²⁺, Cd²⁺, and UO₂²⁺ ions with the same crown ethers–solvent systems. All the resulting 1 : 1 complexes were more stable in nitromethane than acetonitrile solution. In all cases, the stability of both crown complexes in nitromethane and acetonitrile varied in the order Pb²⁺ > Ba²⁺ > Li⁺ > Cd²⁺ > UO₂²⁺.     

Conductance Studies on Complex Formation Between Aza-18-Crown-6 with Ag+, Hg2+ and Pb2+ Cations in DMSO–H2O Binary Solutions

The complexation reactions between Ag⁺, Hg²⁺ and Pb²⁺ metal cations with aza-18-crown-6 (A18C6) were studied in dimethylsulfoxide (DMSO)–water (H₂O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complexes in most cases is 1:1(ML), but in some cases 1:2 (ML₂) complexes are formed in solutions. A non-linear behaviour was observed for the variation of log K _f of the complexes vs. the composition of the binary mixed solvents. Selectivity of A18C6 for Ag⁺, Hg²⁺ and Pb²⁺ cations is sensitive to the solvent composition and in some cases and in certain compositions of the mixed solvent systems, the selectivity order is changed. The values of thermodynamic parameters (ΔH _c^o, ΔS _c^o) for formation of A18C6–Ag⁺, A18C6–Hg²⁺ and A18C6–Pb²⁺ complexes in DMSO–H₂O binary systems were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.     

<Emphasis Type="Italic">N,N</Emphasis>′-bis(<Emphasis Type="Italic">ortho</Emphasis>-acylaryl)diaza-18-crown-6 ethers: Synthesis,complexation in solution,and crystal structure of the complex with lead perchlorate

Two new lariat ethers were obtained from N,N′-diaryldiaza-18-crown-6 (Ar = 2-formyl-4-methylphenyl (II) and 2-benzoyl-4-methylphenyl (III)). In the ethers obtained, the carbonyl O atoms act as additional electron-donating sites. Complexation of lariat ethers II and III with metal cations in solution was studied by ¹H NMR spectroscopy (acetone-d₆, methanol-d₄). The stability constants of the resulting complexes were determined. For lariat ether III and its complexes, the magnetic anisotropy of the benzoyl groups substantially influences the chemical shifts of the protons of the macrocycle. The stability of the complexes increases from ether II to III and in the order K⁺ < Ba²⁺ < Pb²⁺. Complexes with La³⁺ were not obtained. The complex of lariat ether II(L) with Pb(ClO₄)₂, [PbL(H₂O)](ClO₄)₂ · H₂O, was characterized by X-ray diffraction. The Pb²⁺ cation is in the cavity of the lariat ether and is coordinated by the formyl O atoms on one side of the macrocycle plane and by the water molecule on the other side (C.N. 9).     

Study of Complex Formation Between 18-Crown-6 and Pb2+, Tl+ and Cd2+ Cations in Binary Aqueous/Non-aqueous Solvents Using Polarographic Techniques (DPP and SWP)

The complexation of Pb²⁺, Tl⁺ and Cd²⁺ cationsby 18-crown-6 was studied in water/propanol (H₂O/PrOH),water/acetonitrile (H₂O/AN) and water/dimethylformamide(H₂O/DMF) binary systems at 20 °C using squarewave polarography (SWP) and differential pulse polarography (DPP).It was confirmed that the stoichiometry of each of the complexes formed between 18C6 and the respective cations is 1 : 1. The formation constants of the complexes were found to increase with increasing concentration of the non-aqueous solvent. In all cases, a stability order of Pb²⁺ > Tl⁺ > Cd²⁺ was observed. In general,the stabilities of individual complexes were found to decrease as the binary solvent mixture varied from H₂O/AN to H₂O/PrOH to H₂O/DMF.     

Preparation and X-Ray Study of Inclusion Complexes of (4Z,5E)-Pyrimidine-2,4,5,6(1 H,3H)-Tetraone 4,5-Dioxime and the Product of Its Cyclization, (1,2,5)-Oxadiazolo(3,4-d)-Pyrimidine-5,7(4 H,6H)-Dione with Two 18-Membered Macrocycles

The novel dioxime, (4Z,5E)-pyrimidine-2,4,5,6(1H,3H)-tetraone 4,5-dioxime (H₂-PTD) was obtained by the interaction of 6-amino-5-nitrosopyrimidine-2,4(1H,3H)-dione with hydroxylamine hydrochloride. X-ray structural analysis determined the 4Z,5E-configuration of the corresponding monoanion, pyrimidine-2,6(1H,3H)-dione-4-iminole-5-iminolate in the inclusion complexes with diazonia-18-crown-6 (1,4,10,13-tetraoxa-7,16-diazoniacyclooctadecane) (H₂-DA18C6)²⁺ (complex (1), stoichiometry 2 : 1), and its ammonium salt in the complex with the cis-syn-cis isomer of dicyclohexano-18-crown-6(DCHA) (cis-syn-cis-2,5,8,15,18,21-hexaoxatricyclo (20.4.0.0^9,14)hexacosane) (complex (2), stoichiometry 1 : 1). X-ray data were also obtained for the complex of the product of (H₂-PTD) cyclization, (1,2,5)-oxadiazolo(3,4-d)pyrimidine-5,7(4H,6H)-dione (OPD) with diaqua diaza-18-crown-6 (complex (3), stoichiometry 2 : 2 : 1).In (1) the (H-PTD)^- anions are joined into dimers through the bifurcated OH...N and OH...O hydrogen bonds and alternate with diazonia-18-crown-6 cations in the chains sustained by the NH(crown) ... O and NH(crown) ...N interactions. The chains are further combined into the 3D network via NH...O(crown) hydrogen bonds. In (2) the self-complementarity of the (H-PTD)^- anions facilitates their assembly into the chain via OH...N, NH...O and OH...O interactions. The ammonium cations bridge each anion and the DCHA macrocycle with the formation of a ribbon developed along the [101] direction in the unit cell. Ternary complex (3) is built of the neutral species, diaza-18-crown-6, water molecules and dimers of OPD alternated in the chains and held together by OH...O and NH...O hydrogen bonds.     

Stability constants of complexes formed by new Schiff-base lariat ethers derived from 4,13-diaza-18-crown-6 with Ag+, Pb2+, Cu2+ cations determined by competitive potentiometry

The stability of complexes formed by a series of Schiff-base lariat ethers, derived from 4,13-diaza-18-crown-6, 1 with Ag⁺, Pb²⁺, Cu²⁺ cations, has been comparatively determined, in methanol: dichloromethane solution. We present here the synthesis and an interesting competitive potentiometry method useful for the stability constant determination for a new family of Schiff-base bibracchial lariat ethers. The stability constants and the selectivity in competitive complexation of Ag⁺, Pb²⁺ and Cu²⁺ cations by macrocyclic receptors 1–7 (L), can be accurately evaluated and species distribution diagrams can be calculated for individual system. In all cases further functionalization of bibracchial lariat ethers 2–7 is accompanied by an increasing of the selectivity, relative to the complexes of the initial 4,13-diaza-18-crown-6 macrocycle 1.     

Diaquabromo(18-crown-6)rubidium and triaqua(18-crown-6)barium dibromide monohydrate: Synthesis and crystal structures

Two complexes are synthesized: diaquabromo(18-crown-6)rubidium [RbBr(18-crown-6)(H₂O)₂] (I) and triaqua(18-crown-6)barium dibromide monohydrate [Ba(18-crown-6)(H₂O)₃]²⁺ 2Br^? · H₂O (II). The orthorhombic structure of compound I (space group Pnma, a = 10.124 Å, b = 15.205 Å, c = 12.544 Å, Z = 4) and the monoclinic structure of compound II (space group C 2/c, a = 17.910 Å, b = 10.315 Å, c = 14.879 Å, β = 123.23°, Z = 4) are determined by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.063 (I) and 0.042 (II) for all 2293 (I) and 3363 (II) independent measured reflections (CAD-4 automated diffractometer, λMoK _α). The complex molecule [RbBr(18-crown-6)(H₂O)₂] in compound I and the randomly disordered cation [Ba(18-crown-6)(H₂O)₃]²⁺ in compound II are of the host-guest type: their Rb⁺ or Ba²⁺ cation (its coordination number is nine) is located in the cavity of the 18-crown-6 ligand and coordinated by all six O atoms. In structure I, the coordination polyhedron of Rb⁺ is a distorted hexagonal pyramid with a triple apex at the Br^? ligand and two O atoms of the water molecules. In structure II, the Ba²⁺ polyhedron is a distorted hexagonal bipyramid with one apex at the O atom of the water molecule and the other split apex at two O atoms of water molecules.     

Study of Complex Formation Between Dicyclohexano-18-Crown-6 (DCH18C6) with Mg 2+, Ca2+, Sr 2+, and Ba2+ Cations in Methanol–Water Binary Mixtures Using Conductometric Method

The complexation reactions between Mg²⁺,Ca²⁺,Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, dicyclohexano-18-crown-6 (DCH18C6) were studied in methanol (MeOH)–water (H₂O) binary mixtures at different temperatures using conductometric method . In all cases, DCH18C6 forms 1:1 complexes with these metal cations. The values of stability constants of complexes which were obtained from conductometric data show that the stability of complexes is affected by the nature and composition of the mixed solvents. While the variation of stability constants of DCH18C6-Sr ²⁺ and DCH18C6-Ba²⁺versus the composition of MeOH–H₂O mixed solvents is monotonic, an anomalous behavior was observed for variations of stability constants of DCH18C6-Mg²⁺ and DCH18C6-Ca²⁺ versus the composition of the mixed solvents. The values of thermodynamic parameters (ΔH_c°, ΔS_c°) for complexation reactions were obtained from temperature dependence of formation constants of complexes using the van’t Hoff plots. The results show that in most cases, the complexation reactions are enthalpy stabilized but entropy destabilized and the values of thermodynamic parameters are influenced by the nature and composition of the mixed solvents. The obtained results show that the order of selectivity of DCH18C6 ligand for metal cations in different concentrations of methanol in MeOH–H₂O binary system is: Ba²⁺>Sr²⁺>Ca²⁺> Mg²⁺.     

Ethers as ligands. Part VI. Transition metal(II) complexes with 18-crown-6

Summary Seven new coordination compounds are reported with the cyclicpolyether 18-crown-6 as the ligand,viz. [Mg(18-crown-6) (H₂O)₂](SbCl₆)₂, [M(18-crown-6)(MeNO₆)₂](SbCl₆)₂ with M is Ca²⁺ and Sr²⁺, [M(18-crown-6)(MeNO₂)](SbCl₆)₂ with M is Mn²⁺ and Co²⁺, and [M(18-crown-6)](SbCl₆)₂ with M is Ni²⁺ and Zn²⁺.