Synthesis and Complexation Properties of Pyrimidine-Derived Crown Ether Ligands

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.     

Hydrogen-bonded Networks in Crown Ether Complexes of Hydrated Metal Ions

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.     

Photochromism and Metal Complexation of a Macrocyclic Styryl Naphthopyran

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.     

南瓜尼与金属离子的配合作用研究进展

概述了新一代大环主体化合物南瓜尼与金属离子的识别及配合作用的研究进展,包括其超分子配合物的合成方法,晶体结构,键合的热力学性质及其应用前景.     

Synthesis,Structure, Spectroscopic Studies,and Complexation of Novel Crown Ether Butadienyl Dyes

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.     

Study of Host-Guest Complexation of Alkaline Earth Metal Ion,Aluminum Ion and Transition Metal Ions with Crown Ethers by Fast Atom Bombardment Mass Spectrometry

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.     

Regioselective Synthesis of trans-1 Fullerene Bis-Adducts Directed by a Crown Ether Tether: Alkali Metal Cation Modulated Redox Properties of Fullerene–Crown Ether Conjugates

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.     

Complexation Studies of Phosphorus Containing Bis and Tris (Benzocrown Ether) Moieties

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.     

N-取代氮杂冠醚的合成和络合萃取性能研究进展

综述了N-取代氮杂冠醚的合成和对金属离子的选择性络合和萃取研究的新进展.     

Dithiacrown Ether Substituted Porphyrazines: Synthesis, Single-Crystal Structure, and Control of Aggregation in Solution by Complexation of Transition-Metal Ions

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.     

Controlled Growth of Hybrid Halide Perovskites by Crown Ether Complexation for Perovskite Solar Cells

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.     

Synthesis,Metal Ion Complexation Properties,and Electrochemical Behavior of Ferrocenyl Thioacetal Crown Compounds

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.     

氮杂冠醚的Mannich碱合成及其对金属离子的萃取

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...     

Complexation of Silver Ions with Poly(butyl methacrylate) and Propylene Toward Facilitated Propylene Transport

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.     

冠醚改性聚甲基硅氧烷液膜离子传输性能

合成了两种新型的冠醚改性聚甲基硅氧烷，研究了它们作为液膜离子传输载体对离子的传输性能，并考察了膜的稳定性。     

开链冠醚Schiff碱配体与过渡金属离子相互作用研究

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.     

一种冠醚金属卟啉化合物的合成及其阴离子识别机制

本文合成了一种金属冠醚卟啉化合物并提出了一种基于该化合物的阴离子识别机制,为阴离子的可视化识别提供了一种简便的思路。     

二茂钌共轭大环氮杂冠醚的合成及结构

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.D_c=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.