共查询到20条相似文献,搜索用时 15 毫秒
1.
J. T. Y. Redd Jerald S. Bradshaw Peter Huszthy Reed M. Izatt N. Kent Dalley 《Journal of heterocyclic chemistry》1998,35(1):1-8
Five new proton-ionizable macrocyclic ligands containing a pyrimidone-subcyclic unit, 6–10 , were prepared from the previously prepared pyrimidinocrown ethers 1–5 (see Figure 1 and Scheme 1). One of the new proton-ionizable crown ethers is chiral. The proton-ionizable pyrimidonocrown ethers were prepared in high yields by treating the appropriate methoxy-substituted pyrimidinocrown with 5 M sodium hydroxide in a 50% alcohol-water mixture. Complexation properties of four of the pyrimidine-derived macrocycles were studied by various nmr techniques. Pyrimidono-18-crown-6 (9) forms a strong complex with benzylammonium perchlorate and also forms a complex with benzylamine. (S, S)-Dimethyl-substituted pyrimidino- and pyrimidono-18-crown-6 ligands 4 and 9 form stronger complexes with the (R)-form of α-(1-naphthyl)ethylammonium perchlorate than with the (S)-form. (S, S)-Dimethyl-substituted pyrimidono-18-crown-6 ( 9 ) also forms a stronger complex with (R)-α-(1-naphthyl)ethylamine than with the (S)-form. The crystal structure for compound 7 is reported. 相似文献
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Abstract The hydrated metal nitrates (M(NO3)3.6H2O, M[dbnd]Co, Ni, Cu, Zn and Cd) have been crystallised from water in the presence of 18-crown-6 and their structures determined by X-ray crystallography. In the case of copper, a pseudo four-coordinate square planar complex resides in an extended six-coordinate octahedral array which is further bound in a single-stranded one-dimensional hydrogen bonded polymeric mode. For M[dbnd]Co,Ni,Zn and Cd isomorphous complexes are isolated where the octahedral [M(H2O)5(NO3)+ cation resides in a two-dimensional polymeric network through hydrogen bonds between the water ligands and either the crown ether oxygens or unbound nitrate ions or water molecules. 相似文献
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Dr. Elena V. Tulyakova Prof. Dr. Olga A. Fedorova Dr. Jean‐Claude Micheau Dr. Sergey V. Paramonov Dr. Vladimir Lokshin Prof. Stephanie Delbaere 《Chemphyschem》2011,12(7):1294-1301
A macrocyclic benzo‐15‐crown‐5 ether unit tethered to a photochromic naphthopyran by a styryl spacer ( MEN ) is shown to form a 1:1 complex with magnesium(II). The structure and dynamics of the specific host–metal interactions were investigated by PFG‐NMR analysis. A combination of UV/Vis and variable temperature multi‐dimensional 1H NMR photokinetic analysis of the crown‐containing styryl naphthopyran and its metal complex was used to probe the effect of metal complexation on the photochromism. 相似文献
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SergeyP. Gromov ArtemI. Vedernikov EvgenyN. Ushakov LyudmilaG. Kuz'mina AlexeiV. Feofanov VitalyG. Avakyan AndreiV. Churakov YuriiS. Alaverdyan EkaterinaV. Malysheva MichaelV. Alfimov JudithA.K. Howard Bertil Eliasson UlfG. Edlund 《Helvetica chimica acta》2002,85(1):60-81
Butadienyl dyes of the benzothiazole series with various fragments of benzocrown ethers 1a – c were synthesized for the first time. The structures and spectral properties of crown‐containing butadienyl dyes and their complexes with alkali and alkaline‐earth metal cations were studied by X‐ray diffraction analysis and 1H‐NMR, UV/VIS, and resonance Raman spectroscopy. To interpret the experimental results, quantum‐chemical calculations were performed. In the case of Sr2+ and Ba2+ ions, the formation of strong sandwich complexes [M( 1b )2]2+ of an unusual structure involving stacking interactions was established; the dye molecules are arranged one above another in the complex according to the ‘head‐to‐head' pattern. 相似文献
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Complexations of crown ethers with alkali metal ions have been investigated extensively by FAB mass spectrometry over the past decade, but very little attention has been paid to reactions of crown ethers with other classes of metal ions such as alkaline earth metal ions, transition metal ions and aluminum ions. Although fast atom bombardment ionization mass spectrometry has proven to be a rapid and convenient method to determine the binding interactions of crown ethers with metal ions, problems in reliabilities for quantitative measurements of” binding strength for the host-guest complexes have been described in the literature. Thus, in this paper, applications of FAB/MS for investigating the complexation of crown ethers with various classes of metal ions is discussed. Extensive fragmentations for neutral losses such as C2H4O or C2H4 molecules from the host-guest complexes could be observed. The reason is attributed to the energetic bombardment processes of FAB occuring in the formation of these complexes. Complexes of cyclen with metal ions also show neutral losses of C2H4NH molecules leading to fragment ions. Transition metal ions usually form (Crown + MCl)+ type of ions, alkaline earth metal ions can form both (Crown + MCl)+ and (Crown + MOH)+ type of ions. But for aluminum ions, only (Crown + Al(OH)2)+ type of ions could he observed. 相似文献
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Jean-Pascal Bourgeois Luis Echegoyen Monia Fibbioli Ern Pretsch Franois Diederich 《Angewandte Chemie (International ed. in English)》1998,37(15):2118-2121
Regioselective Bingel macrocyclization of C60 with a bis-malonate containing a novel dibenzo[18] crown-6 tether provides a versatile access to trans-1 fullerene bis-adducts such as (±)- 1 . Complexation of a potassium ion by (±)- 1 has a pronounced effect on the redox properties of the carbon sphere as a result of the close proximity of the fullerene surface to the crown ether bound cation, which is enforced by the double bridging. 相似文献
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Christelle Mouveaux Joëlle Levalois-Mitjaville Roger De Jaeger 《Journal of inclusion phenomena and macrocyclic chemistry》2001,39(3-4):253-259
The complexation behaviour between salts of Li+-Rb+ in CD3CN and tris(benzocrown ether)s 2a,bX=P(NMeN=CH-B15C5)3 (X = O, S) and tri[bis(benzocrown ether)][N=P(NMeN=CH-B15C5)2]3
3 was investigated by 13 C NMR spectroscopy. Using the program RMNSTAB, the complexation constants for the different possible complexes (M2L, ML andML2 were L represents one benzo-15-crown-5) were obtained and were compared with those of the corresponding monomer material. A remarkable ``biscrown effect' for compounds 2a,b and 3 was found, especially for potassium and rubidium by the predominant formation of stable ML2 complexes. The strong chelate effect make these ligands highly efficient extracting agents for alkali metal picrate salts of K+, Rb+ and Cs+,as shown by UV-Vis spectroscopy. 相似文献
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van Nostrum CF Benneker FB Brussaard H Kooijman H Veldman N Spek AL Schoonman J Feiters MC Nolte RJ 《Inorganic chemistry》1996,35(4):959-969
The synthesis of novel magnesium, copper, and metal-free porphyrazines, peripherally substituted with dithia-7-crown-2 (MPz(7)), dithia-15-crown-5 (MPz(15)), and dithia-18-crown-6 (MPz(18)) macrocycles is reported. These compounds are prepared starting from dicyanoethylene containing crown ethers 3, 2(1), and 2(2), respectively, which contain sulfur as well as oxygen heteroatoms. The "crowned" porphyrazines bind silver(I) and mercury(II) perchlorates. UV/vis spectroscopy and electron paramagnetic resonance measurements reveal that addition of the transition-metal ions leads to dimerization of the porphyrazine complexes. In the case of the dithia-18-crown-6-substituted porphyrazines, the dimers break up to form monomeric 6:1 guest-host complexes when more than 2 equiv of the metal ion is added. The single-crystal structures of the crown ether 2(2) and the porphyrazine MgPz(18) are presented. Compound C(14)H(20)N(2)O(4)S(2) (2(2)) crystallizes in the monoclinic space group P2(1)/c with a = 10.9310(13) ?, b = 19.383(3) ?, c = 8.6976(14) ?, beta = 108.898(11) degrees, V = 1743.5(5) ?(3), and Z = 4. The structure refinement converged to R = 0.0366 and R(w) = 0.0504. Compound C(56)H(82)MgN(8)O(17)S(8) (MgPz(18)) crystallizes in the triclinic space group P&onemacr; with a = 9.584(3) ?, b = 17.672(2) ?, c = 19.620(4) ?, alpha = 84.904(14) degrees, beta = 85.21(2) degrees, gamma = 89.29(2) degrees, V = 3298.4(13) ?(3), and Z = 2. The structure refinement converged to R1 = 0.0839 and wR2 = 0.2196. The electrical properties of H(2)Pz(18) have been studied by complex impedance spectroscopy. The bulk electrical conductivity of this compound is approximately 1 order of magnitude higher than that of the corresponding 18-crown-6 phthalocyanine. 相似文献
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Sun Ju Kim Ramesh Kumar Chitumalla Jong-Min Kim Joonkyung Jang Jin-Woo Oh Jovana V. Milić Ji-Youn Seo 《Helvetica chimica acta》2023,106(4):e202200193
Host-guest complexation has demonstrated potential for controlling hybrid organic-inorganic metal halide perovskite materials. In particular, crown ethers have been used due to their capacity to interact with metal cations (e. g., Pb2+) and small organic cations (e. g., methylammonium (MA)), which can affect hybrid perovskite materials and their solar cells. However, this strategy has been underexploited in perovskite photovoltaics, and the underlying mechanisms are not well understood. In this study, we investigate the influence of 15-crown-5 ( 15C5 ) and its benzannulated derivative (benzo-15-crown-5, B15C5 ), as well as amino-functionalized analogues (15-crown-5)-2-methylamine, 2A-15C5 , and 4′-aminobenzo-15-crown-5, 4A-B15C5 , on MAPbI3 perovskite crystallization and inverted solar cell performance. We demonstrate the propensity of crown ether modulators to interact with Pb2+ cations at the perovskite interface by density functional theory calculations. This has been shown to facilitate oriented crystal growth and homogeneous film formation, as revealed by X-ray diffraction analysis complemented by scanning electron microscopy. As a result, we demonstrate an increase in the power conversion efficiency of the solar cells of interest to advancing hybrid photovoltaics. 相似文献
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《Journal of Coordination Chemistry》2012,65(1-3):105-112
Abstract Condensation of ferrocenecarboxyaldehyde with dithiols under Lewis acid catalysis produces ferrocenyl thioacetal crown compounds in good to excellent yields. Complexation behavior of several ferrocenyl thioacetal crown compounds toward alkali metal cations, Ag(I), Tl(I), Cu(II), Pb(II) and Zn(II) is assessed by picrate extractions from aqueous solutions into chloroform. Electrochemical behavior of several ferrocenyl thioacetal crown compounds in the absence and presence of sodium ions is investigated by cyclic voltammetry. 相似文献
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氮杂冠醚的Mannich碱合成及其对金属离子的萃取王建华(淮北煤炭师范学院生物化学系淮北235000)关键词合成,Mannich反应,氮杂冠醚,萃取以酚羟基为中心功能基的多齿配体可络合多种金属离子,形成单核或双核金属配合物[1]Nakamura等[2... 相似文献
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Kwi Jong Lee Jae Young Jho Jongok Won Yong Soo Kang 《Macromolecular rapid communications》2002,23(14):839-843
Silver salts are dissolved in poly(butyl methacrylate) to derive polymer electrolytes via coordinative interaction between the silver ion and the carbonyl oxygen atom. The dissolved silver ions react subsequently with propylene to form reversible silver/olefin complexes that can be utilized as olefin carriers for facilitated olefin transport. The complexation behavior and its effects on propylene transport were investigated by means of Raman and FT‐IR spectroscopy, as well as dielectric thermal analysis. 相似文献
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合成了开链冠醚Schiff碱配体H2L(H2L=N,N′-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷).详细研究了该配体在不同溶剂中和过渡金属离子存在下的荧光光谱,探讨了溶剂极性和不同金属离子对其荧光光谱的影响.结果表明:溶剂的极性和金属离子对其荧光性质有较大影响,随着溶剂极性的减小,配体的荧光增强,且谱峰发生蓝移.金属离子Zn2+、Cd2+对配体具有荧光增敏作用,Ni2+、Cu2+具有荧光猝灭作用.探讨了配体与金属离子结合的pH范围,结果显示最佳pH值为7—8. 相似文献
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合成并表征了质子化的N-(二茂钌基甲基)-1,4,7-三氮杂-9-冠-3(1)和N,N′,N″-三-(二茂钌基甲基)-1,4,7-三氮杂-9-冠-3(2).用X射线衍射法测定了化合物2的结构.化合物2的晶体属P21/a空间群.晶胞参数a=1.4285(3)nm,b=1.9888(3)nm,c=1.9133(3)nm;β=109.12(2)°;V=5.1358(1.0)nm3;Z=4.Dc=1.665g/cm3.1和2的核磁共振谱表明,化合物中取代Cp环上质子的共振吸收较二茂钌Cp环上质子的吸收向低场移动.这表明质子化的1,4,7-三氮杂-9冠-3对Cp环上质子具有去屏蔽作用.化合物2的电位扫描曲线在0.84V处出现一个氧化波. 相似文献