Room temperature toluene sensing using phthalocyanine Langmuir-Blodgett films

This study presents the synthesis, characterization and toluene sensing properties of copper(II), indium(III) acetate, mono-lutetium(III) acetate and tin(IV) phthalocyanines substituted with 2,6-dimethoxyphenol bioactive groups at the peripheral and non-peripheral positions. The effects of the substituent's position on the toluene vapor detection capabilities of these compounds were investigated. Adsorption data were analyzed by using first-order and Elovich equations in order to investigate the adsorption kinetics. It was found that the kinetics of the toluene adsorption strongly depends on the position of the substituent groups. Our results showed that the Elovich equation fits the experimental data well for non-peripherally substituted Pc based sensors, while the pseudo first-order model best describes the adsorption data for peripheral substituted Pc based sensors. Some physical, photophysical and photochemical of 2,6-dimethoxyphenoxy substituted metal-free and metallophthalocyanines (indium(III) and zinc(II) Pcs) were investigated by our group [26]. We wondered how copper(II), indium(III), mono-lutetium(III) and tin(IV) Pcs substituted with 2,6-dimethoxyphenoxy bioactive moieties affect the physical, electronic and toluene sensing properties. Hence, highly soluble peripherally and non-peripherally substituted Cu(II), In(III), Lu(III) and Sn(IV) Pcs with 2,6-dimethoxyphenoxy were also synthesized (Scheme 1), and the effects of the position of the substituents and the variety of central metal ions on the their spectroscopic and toluene vapors sensing properties were investigated in this study. KEYWORDS EXPERIMENTAL Materials and Equipment2,6-Dimethoxy-phenoxy substituted phthalonitriles (1 and 2) were obtained by the reaction of 2,6-dimethoxy phenol with 3-nitrophthalonitrile or 4-nitrophthalonitrile through base catalyzed nucleophilic aromatic displacement reaction [26]. All other starting materials and solvents used were obtained commercially. All reactions were carried out under dry nitrogen atmosphere. The novel Pcs (3-10) were successively cleaned by washing with hot acetic acid-water solution by volume 7/3, water, ethanol and acetonitrile in the Soxhlet apparatus. Column chromatography was performed on silica gel 60 for a proper purification of the raw compounds. The purity of the products was tested in each step by thin layer chromotography (Silicagel F-254 coated TLC plate). Melting points of the Pc compounds were found to be higher than 300 °C. IR Spectra and electronic spectra were recorded on a Shimadzu FTIR-8300 (ATR) and a Shimadzu UV-1601 spectrophotometer, respectively. Elemental analyses were performed by the Instrumental Analysis Laboratory of TUBITAK-Ankara. Mass spectra were acquired on a Microflex III MALDI-TOF mass spectrometer (Bruker Daltonics, Germany) equipped with a nitrogen UV-Laser operating at 337 nm in reflectron mode with an average of 50 shots. SynthesisGeneral procedure for the synthesis of metallophth alocyanines (3-10).

Section: Toluene Sensingsupporting

confidence: 91%

Toluene vapor sensing characteristics of novel copper(II), indium(III), mono-lutetium(III) and tin(IV) phthalocyanines substituted with 2,6-dimethoxyphenoxy bioactive moieties

Pişkin

Can

Odabaş

et al. 2018

“…For all the monolayers of aqua aggregates (including face-on structures) the 6. (a) The dependence of area per molecule in an aggregate, (b) degree of initial surface coverage, (c) free water content (per molecule), (d) inter-aggregate spacing and ratio of distance between aggregates to the aggregate diameter in the onset point of a stable state on the initial degree of surface coverage ratio of distance between aggregates at the onset point of the stable state to the aggregate diameter is constant (0.11): (d i /D aggr ) = const (6). For the monolayer of "dry" aggregates this ratio is two-fold higher (Fig.…”

Section: Discussion a Model Of Langmuir Layer Of Copper Tetra-tertbutmentioning

confidence: 99%

“…Floating layers are inhomogeneous and unstable, contain three-dimensional aggregates, and tend to collapse upon compression. Many papers are devoted to azaporphyrines with long side substituents (liquid-crystalline, amphiphilic) [5][6][7][8]. The structure of such azaporphyrines is largely governed by interaction of long peripheral alkyl radicals, causing their molecular assemblies to have stacked structure, which hinders the interaction of azaporphyrine cores [4].…”

Section: Introductionmentioning

confidence: 99%

“…πA-π plots for CuPctBu4, c face = 16 (1), 21 (2), 31 (3) 52 (4), 103 (5), 154%(6). Open circles mark the boundaries of regions corresponding to stable monolayer states of the layer According to the traditional approach to isotherm analysis, this points to the face-on (plane of a molecule is oriented parallel to water surface) orientation of molecules (monolayer).…”

mentioning

confidence: 99%

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Nanoaggregates in floating layers of azaporphyrins

Valkova

Zyablov

Erokhin

et al. 2010

An analysis of compression isotherms of floating layers of copper tetra-tert-butylphthalocyanine (CuPctBu4) and copper tetrabenzotriazaporphyrine, obtained at varied initial conditions, is carried out. The structure of layers is determined by three methods: the traditional one (direct estimation of area per molecule from a π-A isotherm), by a quantitative analysis of compression isotherms (with the use of Volmer equation), and by Brewster angle microscopy. It is shown that in layers with edgeon arrangement of molecules (initial surface concentrations N 0 > 0.15 μmol.m -2 ), the layer structure, determined by the quantitative method, may differ drastically from the structure obtained by the traditional one. The equation of state of the floating layer generalized to the case when structural units of 2D gas are molecular aggregates is used to describe the layer of azaporphyrines. Boundaries of existence and characteristics of structure and properties of floating layers in stable states (size of nanoaggregates formed in a layer, number of molecules in them, interaggregate spacing, compressibility) are determined. The quantitative model of floating layer of copper tetra-tert-butylphthalocyanine is proposed. Constants characterizing a stable monolayer, as well as the region where it may be formed, are determined on the base of the model created.

“…Pcs as a group of potential gas sensing materials, have become a natural choice for the detection of VOCs because of their open coordination sites for axial ligation, their large spectral shifts upon ligand binding and their intense coloration [19]. Previous investigations on Pc thin films as gas sensing materials have revealed a high sensitivity to the various organic vapors [5,[20][21][22][23][24]. Unlike the ensign properties and the effect of environmental conditions on the sensing performance of Pc-based sensors, adsorption kinetics of organic vapors on novel metallophthalocyanine thin films have not been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and VOCs adsorption kinetics of diethylstilbestrol-substituted metallophthalocyanines

Kakı

Gögsu

Altındal

et al. 2019

Compound (4,4[Formula: see text] -hex-3-ene-3,4-diyl)bis(4,1-phenylene)bis(oxy)diphthalonitrile 3 was synthesized by the reaction of 4-nitrophthalonitrile 1 and diethylstilbestrol 2 in dry DMF in presence of dry K2CO3. New mononuclear phthalocyanines 4-6 were obtained from compound 3 by addition of the corresponding metal salts [Co(OAc)2 ⋅ 4H2O, Zn(OAc)2 ⋅ 2H2O and Cu(OAc)2]. The novel compounds were characterized by elemental analysis and FT-IR, UV-vis, 1H-NMR and MALDI-TOF mass spectroscopy techniques. The effects of four main groups of organic vapors on these novel compounds were studied and discussed. The adsorption kinetics of alkanes ([Formula: see text]-hexane and [Formula: see text]-octane), alcohols (methanol and 2-proponal), chlorinated hydrocarbons (dichloromethane and trichloromethane) and amines (diethylamine and triethylamine) on 4-6 were examined using three adsorption kinetic models: the Elovich equation, the pseudo-first-order equations and Ritchie’s equation. Results show that the linear regression analysis with respect to the pseudo-second-order rate equations generates a straight line that best fits the data of adsorption of alcohols and chlorinated hydrocarbons on Pc films. On the other hand, the Elovich equation generates a straight line that best fits the data of adsorption of alkanes and amines.