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Azocalixarenes. 4: synthesis, characterization and investigation of the absorption spectra of hetarylazo-substituted calix[6]arenes
Abstract
Synthesis of seven novel hetarylazocalix[6] arene dyes was achieved by diazotisation of seven different heterocyclic amines using nitrosyl sulphuric acid, coupling with calix[6]arene. Hetarylazocalix[6]arene dyes were characterized based on FT-IR and 1H-NMR spectroscopic techniques as well as elemental analysis. The absorption spectra of the dyes are discussed, both the effect of varying pH and solvent upon the absorption ability of azocalixarenes. Absorption maxima of the prepared dyes showed large bathochromic effects in comparison with analogues dyes containing carbocyclic amine residue. The colour of the azocalixarene dyes is discussed with respect to the nature of the heterocyclic ring and substituents there in. Concentration effects on the visible absorption maxima of the dyes are also reported.
... One application example is the non-mutagenic black ink jet dye [25][26][27][28][29]. As a extension of our previous work in this area [30][31][32][33][34][35][36][37] in this study we report the synthesis of new hetaryltetrakisazobenzidine dyes. ...
... Bordo solid crystal, yield 0. In our earlier studies, carbocyclic and heterocyclic amine substituted azo dyes and some tetrakisazocalix [4]arene derivatives were investigated [30][31][32][33][34][35][36][37]. In this paper, the synthesis of some tetrakisazobenzidine derivatives 3(a-g) has been reported. ...
Objective: The aim of the work was to designed and synthesized novel heterocyclic tetrakisazo dyes.
... However, the color associated with these compounds compromise esthetic quality of water bodies and considered as highly toxic, mutagenic and carcinogenic compounds [3,4] . Many heterocyclic disperse dyes have condensed chromophoric systems with superior shades, high tinctorial strength, excellent color brightness and light fastness stability compared to those derived from non-heterocyclic based components [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] . High fluorescence and good photo-stability of many heterocyclic derivatives have a wide range of application area such as fluorescent dyes, fluorescent brighteners, fluorescent probe and colorimetric chemosensors [21][22][23][24][25][26][27][28][29][30][31][32][33][34] . ...
Six novel fluorescent disperse dyes were synthesized by diazo-coupling reaction. As dye intermediates, two diazo components having 5-amino-4-arylazo-3-methyl-1H-pyrazoles moieties were initially prepared, diazotized and coupled with three pyrrolinone esters (PES) derivatives to give azo-hydrazone pyrazolo/pyrrolinone derivatives. The dye structures were confirmed by FTIR, ¹HNMR, mass spectroscopy and elemental analysis. The absorption spectra of the prepared dyes and its solvatochromic behavior were investigated. These dyes displayed significant emission spectra in polycrystalline (powder) form, but no fluorescence observed in solution. The dyes were applied on polyester fabric using conventional high temperature exhaustion dyeing method, exhibited high tinctorial strength and bright fluorescent orange to reddish violet colors on polyester fabric with dyeing stability under acidic, neutral and alkaline pH. The relationship among different dyeing pH and color difference effects for dyed fabrics were studied. It was found that disperse dyes containing phenylazo-pyrazolone structure showed better dyeing performance and alkali-stable dyeing properties on polyester fabrics than those containing nitrophenol derivatives. The color fastness to washing, perspiration, sublimation and light fastness were also investigated.
... These compounds were prepared by diazotization of six heterocyclic amines using nitrosyl sulphuric acid coupling with calix [4]arene. After that, a series of azocalix [6]arenes (32)(33)(34)(35)(36)(37) and their hetarylazo derivatives by substituting different rings on upper rim were formed and investigated in both the effect of varying pH and solvent upon the absorption ability of hetarylazo calix [6]arenes [11]. The absorption spectra of the dyes were discussed both the effect of varying pH and solvent upon the absorption ability of azocalixarenes (figure 4). ...
An overview of azocalixarene application in analytical chemistry has been surveyed. In this article, some selected
results on the synthesis, chemosensor, and solvent extraction from distinguished works since 2000 up to date will be
presented.
Keywords: absorption properties, azocalixarene, complexation, extraction, chemosensor.
... These compounds were prepared by diazotization of six heterocyclic amines using nitrosyl sulphuric acid coupling with calix [4]arene. After that, a series of azocalix [6]arenes (32)(33)(34)(35)(36)(37) and their hetarylazo derivatives by substituting different rings on upper rim were formed and investigated in both the effect of varying pH and solvent upon the absorption ability of hetarylazo calix [6]arenes [11]. The absorption spectra of the dyes were discussed both the effect of varying pH and solvent upon the absorption ability of azocalixarenes (figure 4). ...
An overview of azocalixarene application in analytical chemistry has been surveyed. In this article, some selected results on the synthesis, chemosensor, and solvent extraction from distinguished works since 2000 up to date will be presented.
... Alternatively, it can be thought that these types of supramolecular structures usually bind or encapsulate solvent molecules into their cavity and thereby prevent to exhibit regular solvatochromic effect [46]. Similar behaviours have been reported for azocaliks [4]arene, azocaliks [6]arene, azoresorsinarene and azoindole and this solvent independent manner of the absorption maxima had been explained by the stability in molecules [38,39,45,47]. It is known that, the ground state for nearly all molecules is less polar than excited state so that a polar solvent will tend to stabilize in the excited state more than ground state [46]. ...
In this study, a convenient method for the synthesis of thirteen novel tetrakisazo dyes containing 25,27-bis-(4-nitrobenzyloxy)-26,28-dihydroxycalix[4]arene have been described. 5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrahydroxycalix[4]arene, 25,26,27,28-tetrahydroxycalix[4]arene and 25,27-bis-(4-nitrobenzyloxy)-26,28-dihydroxycalix[4]arene were synthesized. 2-arylhydrazone-3-ketiminobutyronitriles 1(a–m) were synthesized and reacted with hydrazine hydrate to afford the corresponding 5-amino-4-arylazo-3-methyl-1-H-pyrazoles 2(a–m). Thirteen novel hetaryltetrakisazocalix[4]arene derivatives 6(a–m) were achieved by diazotisation of 5-amino-4-arylazo-3-methyl-1-H-pyrazoles using nitrosylsulphuric acid, coupling with 25,27-bis-(4-nitrobenzyloxy)-26,28-dihydroxycalix[4]arene. The obtained hetaryltetrakisazocalix[4]arene dyes 6(a–m) were characterized based on FT-IR, 1H NMR and Mass spectroscopic techniques as well as Elemental Analysis. The solvatochromic behaviour of these dyes in various solvents was examined. Acid-base effect on the visible absorption maxima of the dyes were also reported.
Bu çalışmada, ilk olarak 5-amino-4-arilazo-3-metil-1-fenilpirazol türevleri
sentezlenmiştir. Elde edilen bu 5-amino-4-arilazo-3-metil-1-fenilpirazol türevleri
daha sonra diazolanarak 5-hidroksi-3-metil-1H-pirazol ve 5-hidroksi-3-metil-1-
fenilpirazol bileşiklerine kenetlenmiş ve yeni pirazol türevi dispers disazo
boyarmaddeleri elde edilmiştir. Sentezlenen bu iki seri boyarmadde element analizi,
UV, FT-IR ve 1H-NMR gibi spektral yöntemlerle karakterize edilmiş ve pH, çözücü
değişimi, elektron alıcı ve elektron verici grupların o-, m- ve p- köşelerinde bağlı
olmasının bu bileşiklerin absorpsiyon yeteneklerini nasıl etkilediği incelenmiştir.
Sentezlenen bu boyarmaddelerin tekstilde kullanımını değerlendirmek üzere
Poliamid 6.6 (P.A. 6.6), Polyester (PES) ve Polilaktikasit (PLA) kumaşlar tüm elde
edilen boyarmaddeler ile boyanmış ve ISO standartlarına göre haslıkları
değerlendirilmiştir.
Macrocyclic compounds play an important role in supramolecular chemistry accounting for their unique recognition and self-assembly properties and potential applications in biomedicine and material science. Azo compounds display promising capability in fields of molecular switches, polymers, smart materials and molecular machines because of their photoactive and electroactive properties. Introducing azo groups into macrocycles gives them signal moieties, additional recognition sites, photo-responsive properties, and so on. Herein, we comprehensively review the structures of azo-containing macrocyclic compounds reported up to now. Then we describe representative works on azo macrocycles with their molecular recognition, self-assembly and application emphasized.
Due to their potential applicability as selective receptors in electrochemical or optical sensors, a bis(azophenol)calix[4]arene derivative H2L has been investigated. The complexation properties of this molecule towards Ni2+ and Co2+ metal ions has been studied. It is revealed that this ligand exhibits tetradentate with N2O2 core when bound to Ni (II) or Co (II) metal ion. The optical response of azo groups of H2L towards Ni2+, Co2+, Cu2+, Pb2+ and Hg2+ metal ions has been investigated in DMSO by UV–vis spectroscopy. The absorption spectra of calix[4]arene with cations show marked changes, especially for Co2+ ion. Furthermore, Job’s plot indicate 1:1 binding-stiochiometry for calix[4]arene with Co2+ ion and Benson-Hilderbrand plot is used for the determination of its association constant. The investigation of UV–vis spectra of chromogenic calix[4]arene in different solvents shows that cis–trans isomerization of azo groups probably depends on kind of solvent. Also the different between the polarity and viscosity of organic solvents used is likely responsible for the changes of the band shape of the spectra.
Novel calix[4]arene/thiacalix[4]arene derivatives bearing arylazo moieties were prepared via a diazo-coupling reaction. Subsequent alkylation with ethyl bromoacetate via the template effect of alkali metal carbonates resulted in arylazo substituted calix[4]arene/thiacalix[4]arene tetraacetates. UV–vis spectroscopy revealed that in terms of their binding affinity towards alkali metal cations, the tetraacetate derivative displayed considerable selectivity for sodium cations (K+Na/KK+>100, K+Na/K+Li>175).
Four new azocalix[4]arenes {5,11,17,23-tetrakis[(2-hydroxy-5-tert-butylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (1), 5,11,17,23-tetrakis[(2-hydroxy-5-nitro phenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (2), 5,11,17,23-tetrakis[(2-amino-5-carboxylphenylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (3) and 5,11,17,23-tetrakis[(1-amino-2-hydroxy-4-sulfonicacidnapthylazo)]-25,26,27,28-tetrahydroxycalix[4]arene (4)} have been synthesized from p-tert-butylphenol, p-nitrophenol, p-aminobenzoic acid and 1-amino-2-hydroxy-4-sulphonic acid by diazo coupling reaction with p-aminocalix[4]arene. The resulting ligands (1–4) were treated with three transition metal salts (e.g., CuCl2·2H2O, NiCl2·6H2O or CoCl2·6H2O). Cu(II), Ni(II) and Co(II) complexes of the azocalix[4]arene derivatives were obtained and characterized by UV-vis, IR,
1H-NMR spectroscopic techniques and elemental analysis. All the complexes have a metal:ligand ratio of 2:1. The Cu(II) and
Ni(II) complexes of azocalix[4]arenes are square-planar, while the Co(II) complexes of azocalix[4]arenes are octahedral with
water molecules as axial ligands. The solvent extraction of various transition metal cations from the aqueous phase to the
organic phase was carried out by using azocalix[4]arenes (1–4). It was found that, azocalix[4]arenes 1, 2 and 3 examined selectivity for transition metal cations such as Ag+, Hg+ and Hg2+. In addition, the thermal stability of metal:azocalix[4]arene complexes were also reported.
The complexing properties of four dimalonate and one diester calix[4]arene derivatives toward alkali and alkaline earth cations have been investigated in acetonitrile by means of UV spectrophotometry. Mononuclear complexes have been detected for all the complexesexcept in the case of ligands 4 and 5 with Na+ and Ca2+ where a biligand species (ML2) is present. This later stoichiometry was also confirmed by 1H-NMR and FAB+ MS methods. In the case of ligand 3 and Sr2+we observed the formation of both mono and binuclear species (ML, M2L). Particular selectivities have to be noted from the unique complexation of Na+ and Ba2+ byligand 2 and Rb+ by ligand 3 toward the two series of cations. The complexation is predominantly dependent on the bulkiness of the cavity and the cation size.
The doubly azobenzene-chain lower-rim substituted calix[4]arenes 6–9 were prepared, followed by the doubly bridged biscalix[4]arenes 10 and 11. All are photoresponsive and detailed studies of the E⇌Z photoisomerization and the Z→E thermal isomerization in 6 and 10 were carried out using UV and 1H NMR spectroscopic techniques. The three (EE, EZ and ZZ) isomers of 6 and 10 were isolated or enriched and fully characterized by 1H NMR. Kinetic analyses of these transformations of 6 were carried out and revealed a concentration dependent behavior and an interesting sequential course of its photoisomerization.
The selective liquid-liquid extraction of various alkaline, alkaline-earth and transition metal cations from the aqueous phase to the organic phase was carried out by using diazo coupling calix[4]arenes [p-(4-n-butyl-phenylazo)calix[4] arene(L1), p-(4-phenylazophenylazo)calix[4]arene(L2), p-(4-acetanilidazo)calix[4]arene(L3), p-(N'-2-thiazol-2-ylsulphanylazo)calix[4]arene(L4) and p-(2-thiazolazo)calix[4]arene(L5)] and the phenol derivatives [2-(5-bromo-2-pyridylazo)-5-diethylaminophenol(L7)] and (2-chloro-4-nitrophenylazo)-5-sec-butyl-2-phenol(L7)]. It was found that compounds L1 - L6 showed some selectivity towards Ag+, Hg+ and Hg2+, while extractability of all cations was observed with compound L2 containing double diazo groups.
Four new double calix[n]arenes (n=4, 5) 2a, 2b, 3a and 3b have been synthesized by coupling reaction of tetrazonium salts 1a and 1b on calix[n]arenes (n=4, 5). The conformation of 2a was studied in solution and in the solid state.
This article describes the synthesis, structure andUV properties of azocalixcrowns in which the photoresponsivetrans-cis azo benzene unit has been introduced in the glycolicchains of the calix[4]crowns. The synthesis proceeded via the selective-1,3O-dialkylation of calix[4]arene with glycolic chains terminated bynitrophenyl residues. After reduction of thenitro groups into amino functions,intramolecular oxidative coupling produced thecapping of the calixarene. Thesynthetic approaches and the cis-transstructure of these new ligandsare discussed and full details on synthesesand structural data are given. Apreliminary example of cesium complexation byone of the ligands is proposed.
The synthesis of azo compounds [4-(N'-2-thiazol-2-ylsulfanyl)-4'-hydroxyazo benzene (1), 4-(N'-2-thiazol-2-ylsulfanyl)-2'-hydroxy-5-tert-butylazobenzene (2), 7-[4-(N'-2-thiazol-2-ylsulfanyl)phenylazo-8-hydroxy quinoline (3)] have been carried out by reacting phenol, 4-tert-butyl phenol and 8-hydroxy quinoline with N'-2-thiazol-2-ylsulfanylamide as coupling component. The resulting ligands (2 and 3) were treated with two transition metal salts (e.g., CuCl22H2O andNiCl26H2O). Cu(II) and Ni(II) complexes of the azo derivative ofphenol were obtained and characterised by IR, UV-Vis, 1H NMR, spectroscopic and elemental analysis techniques. All the complexes have a metal : ligand ratio of 1 : 2 and are square-planar.
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