Synthesis and Spectroscopic Characterization of New Double‐Armed Benzo‐15‐Crown‐5 Derivatives and Their Sodium Complexes

Double‐armed crown ether aldehydes ( 1–3 ) were synthesized from the reaction of 2 equiv salicylaldehyde, 4‐hydroxy‐3‐methoxybenzaldehyde (vanillin), and 3‐hydroxy‐4‐methoxybenzaldehyde (iso‐vanillin) with 4′,5′‐bis(bromomethyl)benzo‐15‐crown‐5. New crown ethers imine compounds ( 4–9 ) were synthesized by the condensation of corresponding crown ether aldehydes ( 1–3 ) with 4‐amino‐1,2‐dihydro‐1,5‐dimethyl‐2‐phenyl‐3H‐pyrazole‐3‐one and 2‐furan‐2‐yl‐methylamine. Sodium complexes ( 1a–9a) of the crown compounds form crystalline 1:1 (Na⁺:ligand) stoichiometries and were also synthesized. The structures of the crown ether aldehydes ( 1–3 ), imine compounds ( 4–9 ), and complexes ( 1a–9a ) were confirmed on the basis of elemental analyses, IR, ¹H and ¹³C NMR, and mass spectrometry. © 2013 Wiley Periodicals, Inc. Heteroatom Chem 24:100–109, 2013; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21070     

Synthesis,Characterization and Redox Properties of Three New <Emphasis Type="Italic">vic</Emphasis>-dioximes and their Nickel(II) Metal Complexes

Three novel vic-dioximes: cyclohexylamine-p-tolylglyoxime (L₁H₂), t-butylamine-p-tolylglyoxime (L₂H₂) and sec-butylamine-p-tolylglyoxime (L₃H₂) were prepared by the reaction of anti-p-tolylchloroglyoxime with cyclohexylamine, t-butylamine and sec-butylamine in absolute THF. The detection of H-bonding in all of the Ni(II) complexes by i.r. revealed the square-planar MN₄ coordination of mononuclear complexes. MN₄ coordination of the [(L₁H)₂Ni] complex was also determined by ¹H and ¹³C-n.m.r spectroscopy. Mononuclear complexes with a 1:2 metal-ligand ratio were prepared using Ni(II) salts. All Ni(II) complexes are insoluble in common solvents. The ligands and complexes were characterized by elemental analyses, FT-i.r., u.v.–vis., ¹H and ¹³C-n.m.r. spectra, magnetic susceptibility measurements, thermogravimetric analyses (t.g.a.) and cyclic voltammetry.     

Secondary metabolites from the aerial parts of <Emphasis Type="Italic">Verbascum dudleyanum</Emphasis> and their biological activities

From the overground parts of Verbascum dudleyanum, six iridoid glycosides, aucubin, ajugol, catalpol, 6-O-α-L-rhamnopyranosylcatalpol, saccatoside, and 6-O-(3″-O-trans-p-coumaroyl)-α-L-rhamnopyranosylcatalpol, and two saponins, ilwensisaponin A and C, as well as a flavonoid, luteolin-7-O-β-glucopyranoside, together with an acetophenone glucoside, picein, were isolated. The structures of isolated compounds were elucidated by spectroscopic methods. These compounds showed biological acitivites. __________ Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 232–234, May–June, 2008.     

Development of an optical fibre reflectance sensor for p-aminophenol detection based on immobilised bis-8-hydroxyquinoline

2,2′-(1,4-Phenylenedivinylene)bis-8-hydroxyquinoline (PBHQ), a highly sensitive reagent used for the colorimetric determination of p-aminophenol (PAP), was successfully immobilised on XAD-7 and coupled with optical fibres to investigate a sensor-based approach for determining p-aminophenol. The solid-state sensor is based on the reaction of PAP with PBHQ in presence of an oxidant to produce an indophenol dye. The reflectance measurements were carried out at a wavelength of 647 nm since it yielded the largest divergence different in reflectance spectra before and after reaction with the analyte. The linear dynamic range of PAP was found within the concentration range of 0.1-2.18 mg l⁻¹ with its LOD of 0.02 mg l⁻¹. The sensor response from different probes (n = 7) gave a R.S.D. of 4.4% at 1.09 mg l⁻¹ PAP concentration. The response time of the optical one-shot sensor was 5 min for a stable solution. As this PAP sensor is irreversible, a fresh sensor has to be used for each measurement. All the experimental parameters were optimized for the determination of PAP. Using the optical sensing probe, PAP in pharmaceutical wastewater and paracetamol was determined. The effect of potential interferences such as inorganic and organic compounds was also evaluated. Potential on-site determination of PAP with such sensors can indirectly aid detection of organo-phosphorus nerve agents and pesticides in the field by inhibition of acetylcholine esterase-catalyzed hydrolysis of p-aminophenyl acetate to p-aminophenol.     

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C₆₀ was used as the complementary hydrogen bonding module (C-1), in which the C₆₀ part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C₆₀ module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C₆₀ module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C₆₀ module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion.     

Syntheses,spectroscopic and crystallographic characterizations of 4-nitrobenzyloxy derivatives and benzofurans from <Emphasis Type="Italic">ortho</Emphasis>-substituted benzaldehydes and 4-nitrobenzyl bromide

A series of benzyloxybenzaldehyde derivatives (1–3) were prepared by the reactions of 4-nitrobenzyl bromide with 4-hydroxy-3-methoxybenzaldehyde (vanillin), 2-hydroxy-3-methoxybenzaldehyde (o-vanillin) and 2-hydroxy-4-methoxybenzaldehyde. When the reaction time is quite long, benzofuran derivatives (4 and 5) were obtained by the reactions of ortho-hydroxyaldehydes with the 4-nitrobenzyl bromide. Condensation reactions among the three benzyloxybenzaldehyde derivatives (1–3) with 2-aminomethylfuran (furfurylamine) yielded the new imine compounds (6–8). The structures of these aldehydes (1–3), benzofuran derivatives (4 and 5) and imine compounds (6–8) were confirmed on the basis of elemental analyses, IR, ¹H NMR and ¹³C NMR and mass spectroscopy. The solid-state structures of compounds 4–6 were determined by single-crystal X-ray crystallography.     

Preparation and spectroscopic characterization of iron(II) and copper(II) complexes of a functionalized crown ether

Condensation between 4′-aminobenzo-15-crown-5- and 4-antipyrinecarboxaldehyde yielded the functionalized crown ether (L = 1,5-dimethyl-4-[(2,3,5,6,8,9,11,12-octahydro-1,4,7,10,13-benzopentaoxacyclopentadecin-15-ylimino)methyl]-2-phenyl-1,2-dihydro-3H-pyrazol-3-one). A 1:1 (Na⁺:L) complex has been prepared. The reaction of Fe(II) and Cu(II) salts with L gave complexes of composition [Fe(L)Cl₂] and [Cu(L)₂Cl₂]. Heteronuclear complexes [Fe(L)Cl₂Na]ClO₄ and [Cu(L)₂Cl₂Na]ClO₄ have also been synthesized from the reactions of [Fe(L)Cl₂] and [Cu(L)₂Cl₂] with NaClO₄. The compounds have been characterized by microanalyses and spectroscopic methods.