Tetrasubstituted copper phthalocyanines : correlation between liquid crystalline properties, films alignment and sensing propertie

Copper phthalocyanines (CuPc) containing alkylthio (-S(CH2)nCH3, n=7 and 15), alkyloxy- (-O(CH2)nCH3, n=7 and 15) and polyoxo (-O(CH2CH2O)3CH3 and -S(CH2CH2O)3CH3) substituents were synthesized and investigated to reveal the effects of substituents type (alkylthio, alkyloxy and polyoxo) and the type of the connecting heteroatom (oxygen or sulphur) on the mesogenic properties, films alignment and sensing behaviour. The liquid crystalline properties of these phthalocyanines were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction techniques. The structure and morphology of spun thin films of copper phthalocyanine derivatives were studied by the UV-Vis and Raman spectroscopies as well atomic force microscopy. The sensing properties of CuPc films were studied by the measurement of conductivity change upon interaction with ammonia in the range 10-50 ppm. All investigated films of CuPc derivatives display thermotropic columnar mesomorphism. It was shown that the films with polyoxo- (-O(CH2CH2O)3CH3 and -S(CH2CH2O)3CH3) substituents as well as with alkylthio -S(CH2)nCH3 (n=7) substituents, which are liquid crystalline at room temperature, form ordered films with a random planar alignment of columns. Their films exhibit the better sensor performance with the maximal sensor response for the films of CuPc containing (-S(CH2CH2O)3CH3) substituents

Stabilization of {Ag₂₀(S^tBu)₁₀} and {Ag₁₉(S^tBu)₁₀} Toroidal Complexes in DMSO: HPLC-ICP-AES, PL, and Structural Studies

The presence of DMSO provides a unique ability to stabilize silver toroidal complexes in the direct reaction between AgStBu and AgNO3 at 80 °C. Slow cooling results in large crystals of [[email protected](StBu)10(DMSO)5.2(NO3)8.2]·3DMSO (1), which were isolated and characterized by single crystal X-ray diffraction (SCXRD) analysis. The crystal structure contains both {Ag20(StBu)10} and {Ag19(StBu)10} clusters. The solution of these material in DMSO was studied with HPLC techniques, which demonstrated the presence of both complexes in solution. The use of [SiW12O40]4– as counter anion gives crystals of a double complex salt [Ag17.8(NO3)3.8(StBu)10][SiW12O40]·30DMSO (2) under the same conditions. Temperature-dependent photoluminescence (PL) was studied

Stabilization of {Ag20(StBu)10} and {Ag19(StBu)10} Toroidal Complexes in DMSO: HPLC-ICP-AES, PL, and Structural Studies

The presence of DMSO provides a unique ability to stabilize silver toroidal complexes in the direct reaction between AgStBu and AgNO3 at 80 °C. Slow cooling results in large crystals of [[email protected](StBu)10(DMSO)5.2(NO3)8.2]·3DMSO (1), which were isolated and characterized by single crystal X-ray diffraction (SCXRD) analysis. The crystal structure contains both {Ag20(StBu)10} and {Ag19(StBu)10} clusters. The solution of these material in DMSO was studied with HPLC techniques, which demonstrated the presence of both complexes in solution. The use of [SiW12O40]4– as counter anion gives crystals of a double complex salt [Ag17.8(NO3)3.8(StBu)10][SiW12O40]·30DMSO (2) under the same conditions. Temperature-dependent photoluminescence (PL) was studied

Tetrasubstituted copper phthalocyanines: Correlation between liquid crystalline properties, films alignment and sensing properties

Copper phthalocyanines (CuPc) containing alkylthio (-S(CH2)(n)CH3, n = 7 and 15), alkyloxy- (-O(CH2)(n)CH3, n = 7 and 15) and polyoxo [-O(CH2CH2O)(3)CH3 and S(CH2CH2O)(3)CH3] substituents were synthesized and investigated to reveal the effects of substituents type (alkylthio, alkyloxy and polyoxo) and the type of the connecting heteroatom (oxygen or sulphur) on the mesogenic properties, films alignment and sensing behaviour. The liquid crystalline properties of these phthalocyanines were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction techniques. The structure and morphology of spun thin films of copper phthalocyanine derivatives were studied by the UV-vis and Raman spectroscopies as well atomic force microscopy. The sensing properties of CuPc films were studied by the measurement of conductivity change upon interaction with ammonia in the range 10-50 ppm. All investigated films of CuPc derivatives display thermotropic columnar mesomorphism. It was shown that the films with polyoxo- [-O(CH2CH2O)(3)CH3 and S(CH2CH2O)(3)CH3]substituents as well as with alkylthio -S(CH2)(n) CH3 (n = 7) substituents, which are liquid crystalline at room temperature, form ordered films with a random planar alignment of columns. Their films exhibit the better sensor performance with the maximal sensor response for the films of CuPc containing (-S(CH2CH2O)(3)CH3) substituents. (C) 2016 Elsevier B.V. All rights reserved.Scientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [108M384]; Russian Science FoundationRussian Science Foundation (RSF) [N 15-13-10014]; Russian Science FoundationRussian Science Foundation (RSF) [15-13-10014] Funding Source: Russian Science FoundationSynthesis of metal phthalocyanine derivatives was carried out under the financial support of the Scientific and Technological Research Council of Turkey (TUBITAK, Project number: 108M384). Development of the technique for investigation of the sensor properties of the films was carried out under the financial support of the Russian Science Foundation (project N 15-13-10014).WOS:0003932537000472-s2.0-8499222209

Heterostructures Based on Cobalt Phthalocyanine Films Decorated with Gold Nanoparticles for the Detection of Low Concentrations of Ammonia and Nitric Oxide

This work is aimed at the development of new heterostructures based on cobalt phthalocyanines (CoPc) and gold nanoparticles (AuNPs), and the evaluation of the prospects of their use to determine low concentrations of ammonia and nitric oxide. For this purpose, CoPc films were decorated with AuNPs by gas-phase methods (MOCVD and PVD) and drop-casting (DC), and their chemiresistive sensor response to low concentrations of NO (10–50 ppb) and NH3 (1–10 ppm) was investigated. A comparative analysis of the characteristics of heterostructures depending on the preparation methods was carried out. The composition, structure, and morphology of the resulting hybrid films were studied by X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission (ICP-AES) spectroscopy, as well as electron microscopy methods to discuss the effect of these parameters on the sensor response of hybrid films to ammonia and nitric oxide. It was shown that regardless of the fabrication method, the response of Au/CoPc heterostructures to NH3 and NO gases increased with an increase in the concentration of gold. The sensor response of Au/CoPc heterostructures to NH3 increased 2–3.3 times compared to CoPc film, whereas in the case of NO it increased up to 16 times. The detection limits of the Au/CoPc heterostructure with a gold content of ca. 2.1 µg/cm2 for NH3 and NO were 0.1 ppm and 4 ppb, respectively. It was shown that Au/CoPc heterostructures can be used for the detection of NH3 in a gas mixture simulating exhaled air (N2—74%, O2—16%, H2O—6%, CO2—4%)

NMR-Relaxometric Investigation of Mn(II)-Doped Polyoxometalates in Aqueous Solutions

Solution behavior of K;5[(Mn(H2O))PW11O39]·7H2O (1), Na3.66(NH4)4.74H3.1[(MnII(H2O))2.75(WO(H2O))0.25(α-B-SbW9O33)2]·27H2O (2), and Na4.6H3.4[(MnII(H2O)3)2(WO2)2(β-B-TeW9O33)2]·19H2O (3) was studied with NMR-relaxometry and HPLC-ICP-AES (High Performance Liquid Chromatography coupled with Inductively Coupled Plasma Atomic Emission Spectroscopy). According to the data, the [(Mn(H2O))PW11O39]5− Keggin-type anion is the most stable in water among the tested complexes, even in the presence of ethylenediaminetetraacetic acid (EDTA) or diethylenetriaminepentaacetic acid (DTPA). Aqueous solutions of 2 and 3 anions are less stable and contain other species resulting from dissociation of Mn2+. Quantum chemical calculations show the change in Mn2+ electronic state between [Mn(H2O)6]2+ and [(Mn(H2O))PW11O39]5−