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1.
A novel tert-butylcalix[4]arene bridged bis double-decker lutetium(III) phthalocyanine (Lu2Pc4) (5) has been synthesized by the reaction of dimeric lutetium(III) phthalocyanine (4) with two equiv. of dilithium octakis hexylthiophthalocyanine in amyl alcohol. The phthalonitrile derivative 1 was obtained through the displacement reaction of 4-nitrophthalonitrile with 1,3-dimethoxy-4-tert-butylcalix[4]arene and was converted to the isoindoline derivative 2 by bubbling ammonia gas in dry MeOH. Compound 4 was prepared from 2, 4,5-bis(hexylthio)-1,2-diiminoisoindoline (3), and lutetium acetate in dry DMF. The new compounds and phthalocyanines were characterized by elemental analysis, IR, UV–Vis, 1H NMR, ESR and MALDI-TOF MS spectra. The electrochemical properties of 4 and 5 have been examined by cyclic voltammetry, and compared. Distinctive differences between the voltammetric behaviour of 4 and 5 were detected. These differences were compatible with the structures of the compounds. A detailed study of the effect of temperature on the d.c. conductivity and impedance spectra (40–105 Hz) of spin coated films of 4 and 5 at temperatures between 290 K and 420 K was carried out. By analyzing the d.c. electrical behaviour of the 5 film, it was found that the experimental data are described by a thermally activated conductivity dependence on temperature with an activation energy of 0.77 eV. The a.c. results give a power law behaviour, σa.c. = A(T)ωs, in which the frequency exponent s decreases with temperature. The sensing behaviour of the film for the online detection of volatile organic solvent vapors was investigated by utilizing an AT-cut quartz crystal resonator. It was observed that the adsorption of the target molecules on the coating surface cause a reversible negative frequency shift of the resonator. Thus, a variety of solvent vapors can be detected by using the 5 film as sensitive coating, with sensitivity in the ppm and response times in the order of several seconds depending on the dipole moment of the organic solvent. 相似文献
2.
Ağırtaş MS Altındal A Salih B Saydam S Bekaroğlu Ö 《Dalton transactions (Cambridge, England : 2003)》2011,40(13):3315-3324
The new mono-nuclear 4-5 and ball-type homo-dinuclear 6 phthalocyanines have been synthesized from the corresponding phthalodinitrile derivative 3. The synthesized compounds have been characterized by elemental analysis, UV-vis, IR,(1)H-NMR and MALDI-TOF-mass spectroscopies. The redox behaviours of the complexes were identified by cyclic voltammetry and square wave voltammetry. The temperature dependence of the electronic properties of compounds and adsorption of SO(2) on thin film of 6 were investigated by conductivity measurements using an interdigital transducer structure on glass substrate. Dc conductivity, measured between 300-475 K, is thermally activated with the activation energy ranging between 0.67 and 0.90 eV. The ac conductivity is found to vary with frequency, ω, as ω(s) in which the frequency exponent s decreases with temperature suggesting a hopping conduction mechanism for all compounds. The SO(2) sensing result showed that the spin coated film of 6 exhibits very good SO(2) sensing properties, fast response and recovery rate, high sensitivity and good repeatability. 相似文献
3.
Zafer Odabaş Ahmet Altındal Ali Rıza Özkaya Mustafa Bulut Bekir Salih Özer Bekaroğlu 《Polyhedron》2007
The new ball-type bisphthalocyanines [metal-free 6, Zn(II) 7 and Co(II) 8] were synthesized from the corresponding 4,4′-[1,1′-methylenebis(naphthalene-2,1-diyl)]bis(oxy)di-phthalonitrile 4, which can be obtained from the reaction of 4-nitrophthalonitrile (2) with 1,1′-methylenedinaphthalen-2-ol 3. A novel clamshell type bisphthalocyanine 5 was synthesized from compound 4 and 4,5-bis(hexylthio)phthalonitrile 1. The novel compounds have been characterized by elemental analysis, UV/Vis, IR, 1H NMR and MALDI-TOF Mass spectroscopies. The electrochemical and spectroelectrochemical measurements showed the formation of various mixed-valence oxidation and reduction species, due to the strong intramolecular interactions between the two phthalocyanine rings, especially in the ball-type phthalocyanines. The conduction properties of the compounds have been examined by d.c. and impedance spectroscopy measurements as function of temperature and frequency. D.c. conductivity, measured between 290 and 480 K, is thermally activated with the activation energy ranging between 0.62 and 0.84 eV. The a.c. results gave a power law behaviour, σa.c. = A(T)ωs, in which the frequency exponent s decreases with temperature for 6, 7 and 8. The bulk resistance of the samples was derived from complex impedance spectra. It was found that the bulk resistance shows a typical negative temperature coefficient of resistance, decreasing with a rise in temperature, like that of a semiconductor. 相似文献
4.
Zafer Odabaş Ahmet Altındal Ali Rıza Özkaya Mustafa Bulut Bekir Salih Özer Bekaroğlu 《Polyhedron》2007
New mononuclear phthalocyanines [Zn(II) 4 and Co(II) 6] and ball-type bisphthalocyanines [Zn(II) 5 and Co(II) 7] have been synthesized from the corresponding compound 3, which can be obtained from the reaction of 4-nitrophthalonitrile 1 with 1a,8b-dihydronaphtho[b]naphthofuro[3,2-d]furan-7,10-diol 2. The novel compounds have been characterized by elemental analysis, UV/Vis, IR, 1H NMR and MASS spectroscopy. The electrochemical measurements show the formation of various mixed-valence oxidized and reduced species, due to intramolecular interactions between the two phthalocyanine units in the ball-type binuclear metallophthalocyanines. Detailed studies of the effect of temperature on the electronic properties of the films were investigated by dc conductivity and impedance spectroscopy techniques at temperatures between 290 K and 460 K. Thermally activated conductivity dependence on temperature was observed from the dc measurements. The ac results give a power law behavior in which the frequency exponent decreases with temperature. It was observed that the impedance spectra consist of a curved line at low temperature. These curved lines transform into a full semicircle with increasing temperature. 相似文献
5.
《Journal of Coordination Chemistry》2012,65(14):1243-1249
A zirconium complex with the p-tert-butylthiacalix[4]arene anion was synthesized and its crystal structure was determined by single-crystal X-ray analysis. The complex [Zr(μ2-CH3OH)(p-tert-butylthiacalix[4]arene)]2·9H2O (1) belongs to the orthorhombic system, space group Pnnm, with a?=?20.436(16), b?=?12.160(8), c?=?20.305(12)?Å, V?=?6774(7)?Å3 and Z?=?2. In Complex 1 zirconium coordinates to four phenolic anions of the deprotonated p-tert-butylthiacalix[4]arene and is bridged by two methanol molecules; the p-tert-butylthiacalix[4]arene adopts a cone conformation. 相似文献
6.
Ozlem SahinMustafa Yilmaz 《Tetrahedron》2011,67(19):3501-3508
Fluorogenic tert-butylcalix[4]arenes bearing two pyrene pendant groups at the lower rim were synthesized. Based on ratiometric changes of monomer and excimer emissions, the pyrene amine derivative of calix[4]arene has been found to act as a selective sensor for Pb2+ and Cu2+ ions, respectively, due to a conformational change upon chelation of these ions. 相似文献
7.
Several new symmetrical aromatic hydrocarbon bridged bipyridine ligands and their binuclear Ru (II) complexes have been designed, synthesized and characterized on the basis of 1H NMR, MS and HRMS. Their absorption and emission properties, electrochemical behaviors and electrochemical luminescence were investigated. All ruthenium complexes show characteristic MLCT absorption and similar redox potential. Among the three complexes reported, 4c has the best electrochemical luminescence property. 相似文献
8.
Salan Ü Altındal A Özkaya AR Salih B Bekaroğlu Ö 《Dalton transactions (Cambridge, England : 2003)》2012,41(17):5177-5187
The new ball-type metallo bisphthalocyanines (Co(2)Pc(2) and Zn(2)Pc(2)) were synthesized from the corresponding [4,4'-bis(dicoumaroylphthalonitrile)] which can be obtained from the reaction of 3,3'-methylenebis(4-hydroxy-2H-chromen-2-one) and 4-nitrophthalonitrile. The structures of the newly synthesized compounds have been confirmed and characterized by elemental analysis, UV/Vis, IR and (1)H NMR spectroscopies and MALDI-TOF mass spectrometry. Solar cells of the configuration ITO/Co(2)Pc(2)/C60/Al and ITO/Zn(2)Pc(2)/C60/Al were fabricated. The effect of the thickness of the active Pc layer--the thickness of the Pc layer was varied from 15 to 80 nm--on solar cells parameters has been investigated. A nearly thickness independent open circuit voltage was observed in both structures. The maximum photovoltaic conversion efficiency, short circuit current and fill factor were observed in ITO/Zn(2)Pc(2)/C60/Al cell with 80 nm Pc layer to be 0.255%, 1 mA cm(-2) and 0.38, respectively. The redox properties of the ball-type complexes were investigated by cyclic voltammetry, controlled-potential coulometry and in situ spectroelectrochemistry in DMSO-TBAP. The electrochemical measurements showed that the complexes form ring-based and/or metal-based mixed-valence species, due to the remarkable intramolecular interactions between the two metal phthalocyanine units. The Vulcan XC-72(VC)/Nafion(Nf)/Co(2)Pc(2) modified glassy carbon electrode showed much higher catalytic performance towards oxygen reduction, compared to the VC/Nf/Zn(2)Pc(2) modified one. It was found that the VC/Nf/Co(2)Pc(2) catalyst is nearly insensitive to the presence of methanol. In the presence of 1 M methanol in the electrolyte, the catalytic performance of the Co(2)Pc(2)-based catalyst in oxygen reduction was much better than that of the Pt-based one. Thus, it was shown that the VC/Nf/Co(2)Pc(2) catalyst can be a good alternative to VC/Nf/Pt as a cathode catalyst in direct methanol fuel cells. 相似文献
9.
2-(2-Aminoethylamino)ethanol (L) reacts with cupric bromide in dimethylformamide to give a mononuclear complex of Cu(II) [L2Cu]Br2, with six-coordinate distorted octahedral geometry, in which two molecules of tridentate (N,N,O) ligand are involved. The structure was confirmed by spectroscopic methods, elemental and thermogravimetric analyses, and magnetic measurements. Optimization of possible configurations indicated the formation of the trans structure of the complex. Experimental results indicate that the investigated complex, bis[2-(2-aminoethylamino)ethanol] copper(II) bromide, behaves as a semiconductor in the studied temperature range of 298–388 K. Gas sensing properties of the film for the volatile organic compounds (VOCs): acetone, tetra-chloromethane, chloroform, ethanol, and methanol, were also investigated as a function of vapor concentration and temperature in dark. The film showed maximum sensitivity to tetrachloromethane and ethanol vapors at room temperature. Responses of the film to the tested gases are reversible. 相似文献
10.
Journal of Inclusion Phenomena and Macrocyclic Chemistry - Newly phthalocyanine derivative which carries 2,6-dimethoxyphenoxy bioactive groups as tetrakis from non-peripheral positions of the... 相似文献
11.
12.
Cemil Alkan Leyla Aras Güngr Gündüz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(19):5692-5698
A diazodiphenylene‐bridged Cu–phthalocyanine polymer was synthesized from the diazonium salt of bensidine and the Cu(II) 1,8,15,22‐tetraaminophthalocyanine complex and characterized with Fourier transform infrared, ultraviolet–visible spectroscopy, and elemental analysis. The polymer was partially soluble in organic solvents such as dimethylformamide and tetrahydrofuran. The molecular weight of the soluble part of the polymer was investigated with ebullioscopy and viscosimetry methods in tetrahydrofuran. Both methods showed that the molecular weight of the polymer was much larger than that of the complex. The conductivity of the samples was measured with a four‐prop conductivity measuring device. Iodine and hydrogen chloride were doped to the polymer, and an increase of about 104 S cm?1 in the electrical conductivity was observed. The cyclic voltammogram of the diazodiphenylene‐bridged Cu–phthalocyanine polymer in contact with a LiClO4 electrolyte exhibited two reductions and two reoxidations with high reversibility and electrochemical stability. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5692–5698, 2006 相似文献
13.
The syntheses of new ball-type Co(II) phthalocyanines containing 4,4′-(9H-fluorene-9,9-diyl)diphenol substituents at non-peripheral (complex 6) and peripheral (complex 7) positions are presented. These complexes were characterized by UV-Vis, FT-IR, mass spectroscopy and electrochemical methods. Both complexes exhibit metal and ring based redox processes, typical of cobalt phthalocyanine complexes. For 6, the metal based reduction was observed at −0.46 V followed by a ring based reduction at −1.40 V. The metal oxidation for 6 was observed at +0.16 V and the ring based oxidation at +1.05 V. For 7, reductions are easier but the oxidations are more difficult. The metal based reduction for 7 was observed at −0.38 V followed by a ring based reduction at −1.03 V. The metal oxidation for 7 was observed at +0.20 V and the ring based oxidation at +1.35 V. 相似文献
14.
通过两个不同的平台合成了一系列结构新颖的硫杂杯[4]芳烃衍生物,阳离子萃取试验表明该硫杂杯[4]芳烃衍生物比含有相似官能团的杯[4]芳烃衍生物具有更好的软金属离子萃取性能,新化合物的结构经IR, 1H NMR,MS和元素分析等证实. 相似文献
15.
Three new binudear cobalt (II) complexes with extended te-tracarboxylato- bridge have been synthesized and characterized, namely [Co2 (PMTA) (bpy)4] (1), [Co2(PMTA)-(phen)4] (2) and [Co2(PMTA) (NO2phen)4] (3), where PMTA represents the tetraanion of pyroniellitic acid, and bpy, phen, NO2-phen denote 2,2'-bipyridine, 1,10-phenan-throline; 5-nirto-1, 10-plienanthroline, respectively. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have PMTA-bridged structures and consist of two cobalt (II) ions, each in a distorted octahedral environment. These complexes were further characterized by variable temperature magnetic susceptibility measurements (4-300 K) and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, giving the exchange integral J = - 1.02 cm-1 for 1, J = -1.21 cm-1 for 2 and J = - 1.18 cm-1 for 3, respectively. These results revealed the operation of antiferromagneti 相似文献
16.
A new naphthalimide derivative of calix[4]arene was synthesized as a highly selective fluorescent compound for Cu2+ among the selected metal ions. This compound was examined for its fluorescent properties toward different metal ions (Na+, Li+, Mg2+, Ni2+, Ba2+, Ca2+, Cu2+, Pb2+, Zn2+) and anions (F?, Cl?, Br?, , , I?, , CH3COO?) by UV, NMR and fluorescence spectroscopy. 相似文献
17.
Novel mono phthalocyanines and cofacial bisphthalocyanines were synthesized from 4,4′-(1a,8b-dihydronaphtho[b]naphthofuro-[3,2-d]furan-7,10-diyl)bis(oxy)diphthalonitrile 1. The products were characterized by elemental analysis, UV-vis, IR, 1H NMR and mass spectroscopy. Both the direct current (dc) and alternating current (ac) electrical properties of the product films were investigated as a function of temperature in the frequency range 40-105 Hz. It was observed that the ac response of the films can be represented by the ωs law. The temperature dependence of dc conductivity showed typical Arrhenius behavior for all compounds. 相似文献
18.
A new imidazolate bridged Cu~(2+),Zn~(2+)binuclear complex[(dtma) CulmZn (dtma)]ClO_4·2.5H_2O taken as active site model for Cu,Zn-SOD has been synthesized and its crystal structuredetermined.All the bond lengths, bond angles and the distance between Cu and Zn atoms in Cu-Im-Zn core of the model complex are close to those in Cu,Zn-SOD.ESR parameters of the modelcomplex as a function of pH show that the imidazolate bridge is stable in pH range 10—12,and isbroken on Zn side at pH~9.With decreasing pH,the imidazole is released at pH~4 and the dtmaligand dissociates from the Cu containing fragment at pH~2.4. 相似文献
19.
The syntheses of new ball-type dinuclear Si(IV)(CH(3)COO)(2) and Ti(IV)O phthalocyanines and two different mononuclear Zn(II) and Ti(IV)O phthalocyanines containing four 1,1'-binaphthyl-8,8'-diol substituents on the peripheral positions are described. The structures of these compounds were characterized using the elemental analyzes, UV-Vis, FT-IR, (1)H NMR and mass spectroscopies. The Φ(F) values are 0.14, 0.10, 0.04, 0.02, 0.07; Φ(T) values are 0.69, 0.71, 0.85, 0.33, 0.71 for 7-11, respectively. All complexes showed very long triplet lifetimes with τ(T) 7510, 3190, 2880, 2370, 9470 μs for 7-11 in DMSO, respectively. 相似文献
20.
We have synthesized a ferrocene-based 1,3-alternate thiacalix[4]arene ditopic receptor 3 that contains four identical polyether arms terminated with the ferrocene amide moieties. Our studies have revealed that this redox-active receptor can be used as an electrochemical sensor to recognize both europium (Eu3+) and dihydrogen phosphate ions with a high selectivity. 相似文献