杯芳烃与NO2硝化反应的研究

系统地研究了羟基杯[n]芳烃、甲氧基杯[n]芳烃和对特丁基杯[n]芳烃(n＝4, 6, 8)与NO₂气体的硝化反应, 发现可以成功地得到25,26,27,28-四羟基杯[4]芳烃、37,38,39,40,41,42-六羟基杯[6]芳烃以及25,26,27,28-四甲氧基杯[4]芳烃的对位全硝化产物, 产率分别为90%, 70%和40%; 尤其是25,26,27,28-四羟基杯[4]芳烃与NO₂的反应20 min即可完成. 认为共振式酚氧负离子结构是影响该类硝化反应的关键, 并对反应机理进行了探讨.     

含酰胺和席夫碱单元的杯[4]芳烃衍生物的合成与配合性能

杯[4]-1,3-二乙酸乙酯衍生物1与水合肼反应生成杯[4]芳烃酰肼衍生物2, 然后进一步与相应的芳醛反应, 高产率地合成了三个新型的含酰胺和席夫碱单元的杯[4]芳烃衍生物3a～3c和一例新型杯[4]冠醚4. 阳离子萃取实验表明新型杯芳烃衍生物比只含有酰胺基或席夫碱基的杯芳烃衍生物有更强的软金属离子配合性能, 杯[4]冠醚4还对Ag^＋有较好的选择性萃取能力.     

硫杂杯[4]芳烃酰胺型氮杂冠醚的合成

硫杂杯[4]芳烃与N,N'-亚乙基双(2-氯乙酰胺)发生分子内"1+1"缩合反应,合成了新型硫杂杯[4]芳烃酰胺型氮杂冠醚--25,27-二羟基-26,28-(1',10'-二氧杂-4',7'-二氮杂-3',8'-二氧代亚癸基)-硫杯[4]芳烃(叔丁基硫杯[4]-1,3-酰胺冠醚)(3),产率68%.1H NMR,ESI-MS和元素分析确证3为1,3-桥联模式且为杯式构象.     

硫杂杯[4]芳烃氧化膦衍生物的合成与晶体结构

合成了部分取代的硫杂杯[4]芳烃氧化膦衍生物, 二(亚甲基二苯基氧化膦)对叔丁基硫杂杯[4]芳烃(化合物1), 培养了化合物的单晶, 用Smart 1000 CCD衍射仪测定了其晶体结构. 结果表明, 1的组成为: C₆₆H₇₀O₆P₂S₄•2CH₃OH, 属三斜晶系, P1空间群, 晶胞参数a＝1.3453(6) nm, b＝1.5289(7) nm, c＝1.7893(9) nm; α＝75.707(9)°, β＝69.131(8)°, γ＝79.734(9)°, Z＝2; V＝3.316(3) nm³, d＝1.215 g/cm³, F(000)＝1288, μ (Mo Kα)＝0.244 mm^－1, R₁＝0.0625, wR₂＝0.1372. 杯芳烃分子采取了锥式构象.     

溶液中杯[4]芳烃双冠-6与Cs~+配位化学研究

研究了溶液中杯[4]芳烃双冠-6(BisC₆)与Cs⁺配位行为.常温下,BisC₆/NPME(邻硝基苯甲醚)体系单级萃铯百分率达99.36%,模拟料液中,Cs⁺/Na⁺和Cs⁺/K²⁺分离系数分别为3.92×10⁴和2.21×10⁴.局域结构模型实验表明,配合物分子中可能存在水或(和)硝酸(根).ESI-MS谱表明,NPME体系中,铯离子与BisC₆同时形成1:1(单核)和2:1(双核)的配合物,并且存在[BisC₆·H₂O],[BisC₆·Cs⁺]⁺,[BisC₆·2Cs⁺·H₂O]₂+和[BisC₆·2Cs₁₀⁺·No₁₀^-3]10⁺等多种配合物分子.EXAFS实验表明,溶液中铯离子的配位数为7,形成7个氧配位的稳定结构,ADF计算验证了EXAFS实验结果.     

基于两种柔性同分异构羧酸配体的钴(Ⅱ)配合物的合成、结构表征及磁性能研究

分别以E-3-[4-(羧甲氧基)-苯基]丙烯酸(H₂L¹)和E-3-[4-(羧甲氧基)-苯基]丙烯酸(H₂L²)为主配体,合成了3种钴(Ⅱ)配位聚合物：[Co(L¹)(bpp)]_n(1),{[Co(μ₃-OH)₂(L²)₄(bpy)₂(H₂O)₄]·12H₂O}_n(2)和[Co(L₂)(bpy)]_n(3)(bpp：1,3-二吡啶基丙烷,bpy：4,4-联吡啶)。通过元素分析、红外光谱、X射线粉末和单晶衍射对其进行了结构表征。结果表明钴(Ⅱ)离子在这3种配合物中具有不同的配位环境,导致3种配合物具有不同的晶体结构和磁性特征。     

多酸导向的间苯二酚杯[4]芳烃[Co8]配位笼的组装及电化学性质

基于多金属氧酸盐（POM）的超分子配位笼的设计和组装引起了广泛的研究兴趣,但在合成过程中仍然存在挑战。本文中,我们报道了一例基于POM-杯芳烃的大型[Co₈]配位笼[Co₈（MTR4A）₆Cl₈]（α-SiW₁₂O₄₀）₂·30DMF·74EtOH （cage-1）,该配位笼由6个碗状间苯二酚杯[4]芳烃（MTR4A）分子、8个Co(Ⅱ)阳离子、2个α-SiW₁₂O₄₀^4-抗衡阴离子和8个Cl^-阴离子组装而成。值得注意的是,α-SiW₁₂O₄₀^4-阴离子通过氢键夹在层与层之间,形成一个三维超分子结构。此外,作为锂离子电池的负极材料,cage-1表现出良好的锂离子存储能力。cage-1也能够实现对亚硝酸盐（NO₂^-）的还原和抗坏血酸（AA）的氧化,是一种具有高活性的双功能催化剂。     

配位聚合物[Co2(C13H10NO2)4(4，4′-bipy)2]n的合成、晶体结构、热稳定性及荧光性质

以N-苯基邻氨基苯甲酸(NPA)、CoSO₄和4,4′-联吡啶为原料,溶液法合成了一个新的配位聚合物[Co₂(C₁₃H₁₀NO₂)₄(4,4′-bipy)₂]_n,并对其进行了红外、元素分析、热重、荧光及X射线衍射等表征与研究。测定结果表明,该配合物晶体属三斜晶系,空间群P1,晶胞参数：a=1.086 99(13) nm,b=1.136 23(13) nm,c=1.414 72(16) nm,α=71.886 0(10)°,β=76.374(2)°,γ=66.177 0(10)°,V=1.507 0(3) nm³,D_c=1.409 g·cm^-3,Z=2,F(000)=662。最终GOF=1.028,最终偏离因子R₁=0.043 7,wR₂=0.079 4。中心Co(Ⅱ)离子分别与2个联吡啶N原子,4个羧基氧原子配位形成六配位的变形八面体结构。其中1个NPA分子的羧基以螯合方式与Co(Ⅱ)金属原子配位,另2个NPA分子的羧基以桥联的方式与相邻的2个Co(Ⅱ)离子配位,形成一个双核Co簇的二级构筑单元。此双核Co簇通过4,4′-联吡啶分子连接起来,最终形成形成一维双链梯状结构。     

两个含吡啶取代苯酚配体的铜配合物的合成与晶体结构

以2-[N,N-二(2-吡啶甲基)氨甲基]-6-醛基-4-甲基苯酚(L)为配体,合成了2个单核铜配合物[CuL(CH₃CN)(ClO₄)]ClO₄(1)和cis-[CuL(NCS)₂]·0.5C₄H₈O₂(2),对它们进行了紫外、红外、质谱、元素分析和单晶结构表征。2个配合物都属于单斜晶系,每个铜均为扭曲的八面体构型。作为四齿配体,L通过2个吡啶氮原子,1个叔胺氮原子和1个酚氧原子和铜离子配位。在配合物1中,乙腈和1个ClO₄参与配位,而在配合物2中2个硫氰根离子为顺式配位。     

Ln(NO3)3·C26H38N2O4(Ln=La、Ce)配合物的合成和La(NO3)3·C26H38N2O4·CH3CN的晶体结构

合成了2个新的希土冠醚配合物Ln(NO₃)₃·C₂₆H₃₈N₂O₄(Ln=La、Ce; C₂₆H₃₈N₂O₄=1, 7, 10, 16-四氧-4，13-二氮杂-N，N′-二苄基环十八烷)。通过元素分析，红外光谱，拉曼光谱及其 ¹H核磁共振谱进行表征。用四圆衍射仪测定了La(NO₃)₃·C₂₆H₃₈N₂O₄·CH₃CN的晶体结构。晶体属三斜晶系，P1空间群，晶胞参数：a=1.2869(4) nm, b=1.5868(6) nm, c=0.9147(2) nm; α=101.89(2)°, β=105.38(2)°, γ=71.96(3)°; Z=2。d_cald.=1.58 g·cm^-3, μ(MoKα)=13.25 cm^-1。中心镧离子与冠醚配体中的4个氧原子和2个氮原子配位，3个硝酸根中的6个氧原子也与La³⁺配位，形成配位数为12的配合物。     

Synthesis,Complexation and Photophysics of 1,3-alternate Calix[4]arene-crowns-6 Bearing Fluorophoric Units on the Bridge

Abstract

Three new calix[4]arene-crown-6 derivatives bearing a fluorophoric unit on the ether bridge were synthesized. All these compounds complex alkali metal picrates in chloroform, and the naphthocrown (2) shows the highest efficiency for cesium ion binding among the calix-crown-6 known so far. Cesium over sodium selectivity is remarkably higher in acetonitrile than in chloroform solution. ¹H NMR studies, carried out in CDCl₃ on the cesium picrate complex of ligand 2, show that the anion is involved in a π-π stacking with the naphthyl unit The lariat calix[4]-crown-6 (4) does not show any relevant change in absorption and fluorescence spectra upon cesium binding, thus indicating that the dansyl unit is not perturbed by metal ion complexation. On the contrary, for ligands 2 and 3 a luminescence intensity decrease is observed upon cation binding, which allows an easy detection of cesium even at very low concentrations (10^?7M).     

Novel Cesium‐Selective Electrodes Based on Lipophilic 1,3‐Bisbridged Cofacial‐calix[6]crowns

Five bisbridged calix[6]crowns have been investigated as Cs⁺ ionophore in PVC membrane electrodes. As ionophores, three 1,3‐bisbridged calix[6]crown‐4‐ethers( I–III ), 1,3‐bisbridged calix[6]crown‐5‐ether( IV ), and 1,3‐bisbridged calix[6]crown‐6‐ether( V ) have been evaluated. The membranes all give good Nernstian response in the concentration range from 1×10^?7 to 1×10^?1 M of cesium ion. The best detection limits (?log aequation/tex2gif-inf-1.gif=7.08–7.36) are obtained for electrode membranes containing 1,3‐bisbridged cofacial‐calix[6]crown‐4‐ethers( I‐III ), and the values are the lowest compared with those reported previously. The highest selectivity coefficients [ 3.74(Cs/K), 2.63(Cs/Rb)] are obtained for the membrane of 1,3‐bisbridged calix[6]crown‐4‐ether( II ), and these values are also the highest compared with previous reports for Cs⁺‐ISEs. The highest selectivity towards cesium ion is attributed to the geometrically cofacial positions of two crown‐ethers in calix[6]crowns in order to provide the complex of cesium ion and eight oxygens of cofacial crowns.     

腙型双冠醚对碱金属的配位性能

本文报道了五个腙型双冠醚的合成。电导测定结果表明含苯并-15-冠-5单元的双冠醚与四苯基硼酸钾、铷、铯,含苯并-18-冠-6单元的双冠醚与四苯基硼酸铯生成2:1夹心型配合物(冠醚单元:金属离子)。并用这些双冠醚的氯仿溶液萃取苦味酸碱金属盐水溶液,测定了萃取百分率和计算了萃取平衡常数,结果表明腙型双冠醚的萃取能力及选择性优于相应的单冠醚。     

A study of the hydration of the alkali metal ions in aqueous solution

The hydration of the alkali metal ions in aqueous solution has been studied by large angle X-ray scattering (LAXS) and double difference infrared spectroscopy (DDIR). The structures of the dimethyl sulfoxide solvated alkali metal ions in solution have been determined to support the studies in aqueous solution. The results of the LAXS and DDIR measurements show that the sodium, potassium, rubidium and cesium ions all are weakly hydrated with only a single shell of water molecules. The smaller lithium ion is more strongly hydrated, most probably with a second hydration shell present. The influence of the rubidium and cesium ions on the water structure was found to be very weak, and it was not possible to quantify this effect in a reliable way due to insufficient separation of the O-D stretching bands of partially deuterated water bound to these metal ions and the O-D stretching bands of the bulk water. Aqueous solutions of sodium, potassium and cesium iodide and cesium and lithium hydroxide have been studied by LAXS and M-O bond distances have been determined fairly accurately except for lithium. However, the number of water molecules binding to the alkali metal ions is very difficult to determine from the LAXS measurements as the number of distances and the temperature factor are strongly correlated. A thorough analysis of M-O bond distances in solid alkali metal compounds with ligands binding through oxygen has been made from available structure databases. There is relatively strong correlation between M-O bond distances and coordination numbers also for the alkali metal ions even though the M-O interactions are weak and the number of complexes of potassium, rubidium and cesium with well-defined coordination geometry is very small. The mean M-O bond distance in the hydrated sodium, potassium, rubidium and cesium ions in aqueous solution have been determined to be 2.43(2), 2.81(1), 2.98(1) and 3.07(1) ?, which corresponds to six-, seven-, eight- and eight-coordination. These coordination numbers are supported by the linear relationship of the hydration enthalpies and the M-O bond distances. This correlation indicates that the hydrated lithium ion is four-coordinate in aqueous solution. New ionic radii are proposed for four- and six-coordinate lithium(I), 0.60 and 0.79 ?, respectively, as well as for five- and six-coordinate sodium(I), 1.02 and 1.07 ?, respectively. The ionic radii for six- and seven-coordinate K(+), 1.38 and 1.46 ?, respectively, and eight-coordinate Rb(+) and Cs(+), 1.64 and 1.73 ?, respectively, are confirmed from previous studies. The M-O bond distances in dimethyl sulfoxide solvated sodium, potassium, rubidium and cesium ions in solution are very similar to those observed in aqueous solution.     

Cesium Complex of an Unsymmetrical Calix[4]crown-dibenzocrown-6

An unsymmetrical calix[4]-bis-crown ether having both conventional crown-6 and dibenzocrown-6 rings in a fixed 1,3-alternate conformation was synthesized with good yield by the reaction of a monocyclic calix[4]crown-6 with dibenzodimesylate in the presence of cesium carbonate. The cesium ion selectivity among alkali metal ions increased compared to symmetrical calix[4]-bis-crown-6. The solid state structureof the ligand-cesium complex illustrates a 1:2 complex ratio. On the contrary, insolution, e.g., extraction equilibrium and ¹H NMR experiment gave a 1:1 complex ratio. From the result of the chemical shift change upon metal ion complex, the cesium ion seems to prefer the dibenzocrown loop to the conventional crown-6 ring.     

First Synthesis of 1,3-Alternate 25,27-Dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 as New Cesium Selective Extractants by Suzuki Cross-coupling Reaction

The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a–f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using ¹H, ¹³C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a–f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media.     

Strukturen der Alkalimetallsalze aromatischer,heterocyclischer Amide: Synthese und Struktur von Kronenether‐Addukten der Alkalimetall‐indolide

Structures of Alkali Metal Salts of Aromatic, Heterocyclic Amides: Synthesis and Structure of Crown Ether Adducts of the Alkali Metal Indolides The synthesis of five alkali metal indolide crown ether complexes is reported. Lithium‐indolide(12‐crown‐4) ( 1 ) was synthezised from butyllithium, indole, and 12‐crown‐4; sodium‐indolide(15‐crown‐5) ( 2 ) from sodium metal, indole, and 15‐crown‐5; potassium‐indolide(18‐crown‐6) ( 3 ) from potassium hydride, indole, and 18‐crown‐6. Rubidium‐ and cesium‐indolide(18‐crown‐6) ( 4 , 5 ) were made from Rb‐ and Cs‐hexamethyldisilazide, indole, and 18‐crown‐6. The structures of 2 , 4 , and 5 could be determined by X‐ray diffraction. The complexes 2 and 4 are mononuclear, the indolide anion shows an η¹(N)‐coordination to the metal cation. Complex 5 is dinuclear with a central [Cs—N—]₂‐ring.     

镝与二甘醇酸的配位聚合物的水热合成、晶体结构及荧光性质

DyCl₃·6H₂O与二甘醇酸(H₂dga)在水热条件下反应得到配位聚合物{[Dy₂(dga)₃(H₂O)₄]·2H₂O}_n，用X-射线衍射单晶结构分析方法确定了其晶体结构。该配合物的晶体属于正交晶系，C222₁空间群。在配合物中，Dy³⁺离子存在两种类型的配位环境。九配位的Dy1离子与3个二甘醇酸根的6个羧基氧原子和3个醚氧原子配位，其配位多面体可描述为一个扭曲的单帽四方反棱柱;八配位的Dy2离子周围的8个配位氧原子形成一个扭曲的四方反棱柱配位多面体，其中4个氧原子来自4个二甘醇酸根，另外4个氧原子由4个配位水分子提供。二甘醇酸配体的2个羧基和其醚氧原子同时与Dy³⁺离子配位而形成2D网状结构。 该配合物在室温下的固体荧光光谱显示了中心Dy³⁺离子的特征荧光，位于483 nm和574 nm的发射峰分别对应于Dy³⁺离子的 ⁴F_9/2 → ⁶H_15/2和 ⁴F_9/2 → ⁶H_13/2跃迁。     

Hochdrucksynthese von Caesiumamidazid,Cs2(NH2)N3 aus Caesiummetall und Ammoniak

High-pressure Synthesis of Cesium Amide Azide, Cs₂(NH₂)N₃ from Cesium Metal and Ammonia The reaction of cesium and yttrium metal with ammonia at 5–6 kbar and 190–220°C led to a well crystallized cesium amide azide and to YN. The formation of the cesium compound is discussed by volume effects. X-ray investigations gave the atomic arrangement of the compound. The tetragonal unit cell with a = 8.194(3) and c = 4.450(1) Å contains two formula units. The structure determination was successfull in the space group P4/mbm. The azide ion has different coordination and bond length (1.255 Å) as compared with that in the alkali metal azides (1.17 Å). The amide ions carry out a strong libration.