Synthesis and Crystal Structure of 〔Na(N-(p-chlorophenyl)aza-15-crown-5)-(Et_2O)〕_2 (Na_2W_(0.5)Mo_(7.5)O_(26))

[Na (N- (p-chlorophenyl ) aza-15--crown--5 ) (Et2O )]2 (Na2W0.5 Mo7.5 O26), Mr= 2119. 4, monoclinic, space group P21/c, a= 17. 803(4), b= 13. 674 (3), c= 14. 610(3), β= 112. 33(3)°, V=3290(1) A3, Z= 2, Dc= 2. 139 g/cm3, μ= 1.704 mm-1, F (000) = 2079, R = 0. 026, Rw= 0. 030. The supermolecular complexconsists of one [Na2W0.5Mo7.5O28)2- anion in which only two Mo atoms are replaced byW in 25% (M= l/4W+3/4Mo) and the two Na+ are linked symmetrically to neighbouring [W0.5Mo7.5O26]4- units on the right and the left respectively and two complexcanons in which each Na+ deviates from the plane of the four ether oxygens and is coordinated to every hetero--atom in the crownether ring, and is also coordinated to the Oatom of Et2O.

Metal Ion Enhanced Phosphorescence of 2,3-Naphtho-10-aza-15-crown-5: A Possible Molecular Photonic Operator

A novel crown ether, 2,3-naphtho-10-aza-15-crown-5 (NAC) was synthesized.This compound does not show strong fluorescence and phosphorescence due to photoinducedintramolecular electron transfer from the nitrogen lone pair of electrons to the singlet excitedstate of the naphthalene chromophore. Complexation with heavy-metal ions results in the quenching ofthe fluorescence and enhancement of the phosphorescence significantly. These observations wereinterpreted in terms of the binding interactions, between the nitrogen lone pair electrons and themetal cation, which prevent photoinduced intramolecular electron transfer, and the heavy-atomeffects which induce quenching of the fluorescence and enhancement of the phosphorescence. Theseazacrown and heavy-metal-based systems could be useful as potential chemical sensors and molecularphotonic devices.

Synthesis of Unsymmetrical Bissalicylaldimine Ligands and bis-Schiff Base Cobalt Complexes with Benzo-10-aza-15-crown-5 Pendant

Novel unsymmetrical bissalicylaldimine bis-Schiff bases with a benzo-10-aza-15-crown-5 pendant and their cobalt complexes have been synthesized via condensation of 3 or 5-[（benzo-10-aza-15-crown-5）-10-ylmethyl] salicylaldehyde with the half unit Schiff bases and characterized by ^1H NMR, IR, mass spectroscopy, elemental analysis, molar conductances and molar magnetic susceptibility.

Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal

Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.

The Novel Benzo-15-Crown-5 with Palladium(II) Complex: [Na(B15CS)]_2,[Pd(SCN)_4]

A novel Pd(II) Benzo-15-crown-5 complex [Na(B15CS)]_2[Pd(SCN)_4] has been isolated and characterized by IR and X-ray diffraction analysis. The crystal structure belongs to monoclinic, space group P2_1,/n with cell dimensions, a = l.0164(6), b = l.3743(3), c = l.4987(7) nm, β = 95.248(6) °, V = 2.0847 'nm_3, Z = 2, F(000) = 944, R = 0.053, Rw = 0.072. The compound consists of two [Na(B15CS)]+ complex canons and a [Pd(SCN)4_]^(2-) complex anion. Each sodium ion is coordinated by five crown ether oxygen atoms and one N atom from the SCN group of [Pd(SCN)_4]^(2-) to form stable neutral complex.

Dioxygen affinities and catalytic oxidation performance of cobalt(Ⅱ) hydroxamates with benzo-15-crown-5 pendants

The oxygenation constants （Ko2） of cobalt（Ⅱ） hydroxamates （CoL^1 2-CoL^3 2） with benzo-15-crown-5 （B15C5） pendants were measured over the range of -5 to ＋20 ℃, and the values of thermodynamic parameters （ΔH^0 and ΔS^0） were calculated based on these （Ko2） values, Meanwhile, these crowned complexes were employed to the oxidation for p-xylene to p-toluic acid with air at 110Δ under normal atmospheric pressure. The effects of B15C5 pendant and the length of chain bonded to B15C5 in these complexes on the O2-binding capabilities and oxidation for p-xylene were investigated with the comparison of crown-free analogues CoL^4 2.

STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(Ⅳ)SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 4'-BROMO-5'-NITROBENZO-15-CROWN-5

Six new solid complexes of macrocyclic polyether ligand 4′-bromo-5′-nitrobenzo-15-crown-5(L)with Uivalent rare earth nitrates having composition of RE(NO_3)_3·L·mCH_3CN·nH_2O(RE=L_a--Nd,m=n=0, RE=Sm,Bu,m=0.1,n=1,4)have been synthesized in acetonitrile or acetone.All the isolated complexes have been char- acterized by elementary analysis,IR and UV spectra,differential thermal and thermogravimetric analysis,X-ray powder diffraction analysis,molar conductance and measurementa of solubility in some general solventa.It shows that coordination number of the rare earth cation in the complexes of La,Ce,Pr and Nd nitrate is eleven.

STUDIES ON HETERO-MACROCYCLIC POLYETHER(1).THE SYNTHESIS OF 10-SELENA BENZO-15-CROWN-5

The synthesis of a new type of hetero-macrocyclic polyether 2,3-henzo-1,4,7,13-tetraoxa-10-selenacyclopentadeca-2-ene is deseribed.

STUDISS ON HETERO-MACROCYULIC POLYETHER(Ⅲ).THE SYNTHESES OF 10-TELLURABENZO-15-CROWN-5 AND ITS PLATINUM COMPLEX AS WELL AS ITS CATALYTIC BEHAVIOR IN HYDROSILYLATION

The syntheses of a new type of heteromacrocyclic polyether- 2,3-benzo-1,4,7,13-tetraoxa-10-telluracyclopentadeca-2-ene(L),and its pla- tinum complex(PtL_2Cl_2)were described.The catalytic activity of this complex for the hydrosilylation of olefins by triethoxysilane was investigated.

STUDIES ON HETERO-MACROCYCLIC POLYETHER (Ⅱ). THE SYNTHESIS OF PLATINUM COMPLEX OF 10-SELENABENZO-15-CROWN-5 AND ITS CATALYTIC BEHAVIOR IN HYDROSILYLATION

The title complex (PtL_2Cl_2) was synthesized by reacting 10-selenabenzo-15-crown-5 (L) with potassium chloroplatinite. Its catalytic activity for the hydrosilylation of olefins by triethoxysilane, was investi gated.

4-(氮杂-15-冠-5)-1,8-萘酰亚胺荧光探针的合成及性能研究

N-丁基-4-溴-1,8-萘酰亚胺与二乙醇胺反应,合成了N-丁基-4-二(2-羟乙基)氨-1,8-萘酰亚胺,进一步与对甲基苯磺酸二缩三乙二醇双酯反应合成了N-丁基-4-(氮杂-15-冠-5)-1,8-萘酰亚胺.用NMR,IR,MS等表征了产物结构.该化合物在二氯甲烷溶液中识别Li+和Na+,识别后吸收光谱和荧光光谱蓝移.

苯基氮杂-15-冠-5对钼同多酸以及钨钼杂多酸阴离子的选择

合成了两种氮杂大环八聚多酸超分子配合物［Na（N-Ph）aza-15C5（Et2O）］2Na2MO8O26（Ⅰ）和［Na（N－Ph）aza－15C5（Et2O）］2Na2Wo25Mo7.75O26（Ⅱ），用元素分析、IR、1HNMR和H，H－COSY谱进行了表征，并用X射线测定了配合物（Ⅱ）的晶体结构．配合物（Ⅱ）属单斜晶系，空间群为P21/c，晶胞参数为：a=1.7644（4）nm，b=1．3702（3）nm，c=1．4507（3）nm，β=114．02（3）°，Z=2．该类晶体由大环金属销配位阳离子和二维阴离子网络［Na2WxMo8-xO26」2-组成，阴、阳离子分层堆积．研究了苯基氮杂-15-冠-5和与之键合的多酸阴离子的结构及相互关系．发现在苯基氮杂-15-冠-5分别与八错多酸和六聚钨错杂多酸反应所得的产物中，多酸阴离子的聚合度均为8．表明大环化合物的结构与阴离子的结构有一定的对应关系．

苯并-10-氮杂-15-冠-5取代的单Schiff碱的合成及其锰(Ⅲ)配合物的催化环氧化性能

由苯并 10 氮杂 15 冠 5经Mannich反应、还原和缩合制得了含单氮杂冠醚的水杨醛亚胺单Schiff碱HL1和HL2.研究了它们的锰(Ⅲ)配合物MnL21Cl和MnL22Cl的仿酶催化性能,并与非冠醚类似物MnL23Cl比较,考察了配体芳环上挂接氮杂冠醚环对锰(Ⅲ)配合物的催化环氧化性能的影响.结果表明,在常温常压下,MnL21Cl和MnL22Cl比MnL23Cl具有更高的催化活性.其中,具有正庚氧基的MnL22Cl最佳,苯乙烯转化率52.6%,环氧化选择性96.2%,摩尔转化频率(TOF)17.5h-1.

N-对氯苯基氮杂15冠5八钼多酸钠超分子配合物的结构与热分解

本文对新型超分子配合物［Ｎａ（Ｎ（ｐＣｌＰｈ）１５Ｃ５（Ｅｔ２Ｏ）］２Ｎ２Ｍｏ８Ｏ２６进行了Ｘ射线四圆衍射测定，该晶体属单斜晶系，空间群为Ｐ２１／ｃ，ａ＝１．７８０３（４），ｂ＝１．３６７４（３），ｃ＝１．４６１０（３）（ｎｍ），β＝１１２．３３（２）°，Ｖ＝３．２９０（１）ｎｍ３，μ（ｍ）（ＭｏＫａ）＝２０２１．３，Ｄｃ＝２．１４ｇ／ｃｍ３，μ＝１．７１ｎｍ－１，Ｆ（０００）＝２０７９．６３，Ｒ＝０．０２５６和ＲＷ＝０．０２９５，并联系差热热重分析和１ＨＮＭＲ实验，讨论了配合物的热分解过程。

苯基氮杂-15-冠-5-八钼多酸钠超分子配合物的结构与热分解

本文对新型超分子配合物［Ｎａ（ＮＰｈ）１５Ｃ５（Ｅｔ２Ｏ）］２Ｎａ２Ｍｏ８Ｏ２６进行了Ｘ射线四园衍射测定，该晶体属单斜晶系，空间群为Ｐ２１／ｃ，ａ＝１７８０３（４），ｂ＝１３６７４（３），ｃ＝１４６１０（３），β＝１１２３３（２）°，Ｖ＝３２９０（１）ｎｍ３，Ｍｒ＝２０２１３，Ｄｃ＝２１４ｇ／ｃｍ３，μ＝１７１ｍｍ－１，Ｆ（０００）＝２０７９６３，Ｒ＝００２５６和Ｒｗ＝００２９５，并联系差热热重分析和１ＨＮＭＲ实验，讨论了配合物的热分解过程．

带取代酮基的中性生色氮杂15-冠-5-醚的合成及其络合性质的研究

通过艹卓酚酮甲基醚的取代衍生物与氮杂15 冠 5 醚的缩合反应,除了得到文献已报道的化合物2a以外,还得到了两种新的带取代艹卓酮环的中性生色氮杂15 冠 5 醚.用1HNMR和MS表征了其结构,并利用UV Vis光谱评价了三种化合物对Na+、K+、NH4+的络合性能.

9-Benzylidene-9H-fluorene Derivatives Linked to Monoaza- 15-crown-5： Synthesis and Metal Ion Sensing

Two kinds of novel styryl chemosensory 2-FMNC and 3-FMNC, were designed and synthesized by an apporiate introduction of 9-benzylidene-9H-fluorene group as fluorophore with the aim at avoiding photoisomerisation. These 9-benzylidene-9H-fluorene derivatives showed the similar selectivity and sensitivity upon addition of metal ions. The sensitivity of FMNC to alkaline earth metal ions was Ba2＋〉 Sr2＋〉Ca2＋≈Mg2＋.

Construction of a PVC based 15-crown-5 electrochemical sensor for Ag(Ⅰ) cation

The macrocyclic ligand,15-crown-5,was used as an ionophore for fabrication of a polyvinyl chloride（PVC） based membrane sensor for Ag（Ⅰ） cation.For construction of the Ag（Ⅰ） cation selective electrode the best response characteristics were obtained using the composition： 15-crown-5/PVC/o-nitrophenyloctylether（NPOE）/sodium tetraphenyl borate（NaTPB） in the percentage ratio of 5.6/30/60.5/3.9（w/w/w/w）.The electrochemical sensor shows a linear dynamic range 1.0 10 7–1.0 10 1mol/L and a Nernstian slope of 58.9 0.5 mV/decade with a detection limit of 8.09 10 8mol/L for Ag（Ⅰ） cation.It has a fast response time of 〈10 s and can be used for at least 8 weeks without any considerable divergences in its potential response.It was successfully used as an indicator electrode in potentiometric titration of Ag（Ⅰ）cation with I and Cl anions and also for the determination of this metal cation in radiology waste water.

氮杂冠醚取代的单Schiff碱的合成及其钴(Ⅱ)配合物的氧加合性能

由苯并 10 氮杂 15 冠 5出发 ,经 2～ 4步反应合成了氮杂冠醚取代的单Schiff碱HL1,HL2及其异构体HL3 ,HL4.并以元素分析 ,IR ,1 HNMR和MS进行了表征 .在不同温度下 ,测定了它们的钴 (Ⅱ )配合物的氧合反应平衡常数及热力学参数ΔH°和ΔS° ,并与合成的非冠醚类似物CoL2 5 ,CoL2 6和CoL2 7比较 。