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

Abstract

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).

Synthesis, spectroscopy, and photophysical properties of newly magnesium (II) phthalocyanine

“…Precursor molecule 1 for this reaction were synthesized as given in literature [28][29][30][31][32]. The MgPc 2 was synthesized by cyclotetramerization reaction of the 4-(2,6-dimethoxy phenoxy)phthalonitrile 1 presence of DMAE as the solvent, DBU as the catalyzer and anhydrous magnesium(II) chloride under the nitrogen atmosphere (Scheme 1).…”

“…Main findings are found suitable for proposed structure of this phthalocyanine. The proposed target structure of the MgPc 2 was affirmed in the FT-IR spectra by the disappearance of the -C≡N vibration at 2231 cm −1 for the phthalonitrile 1 [28][29][30][31][32]. In the FT-IR spectrum of the MgPc 2, stretching vibrations of aromatic CH groups around 3065 cm −1 , aliphatic-CH, CH2 groups around 2970-2850 cm −1 , aromatic -C=C groups around 1596 -1582 cm −1 and -C-H bands around 1480-1450 cm −1 appeared at expected frequencies (Fig.…”

Novel indium(III) acetate phthalocyanine: synthesis and spectroscopic properties

“…Therefore, they have different advanced technological application areas. The main areas of use are electrochemical applications [10,11], gas sensors [12,13], pigments and dye industry [14,15], photovoltaic materials [16,17], liquid crystals [18,19], organic field transistors [20][21][22], non-linear optical materials [23][24][25], light-emitting devices [26,27], optical switching and limiting devices [28][29][30], solar cells [31,32] and as a photosensitizer for photodynamic therapy (PDT) [33][34][35][36][37][38][39][40][41]. The type of metal in the metal-containing phthalocyanine (MPc) cavity, changes MPc's planar geometry, solubility, thermal and optical stability, as well as electrical and chemical properties [42][43][44][45][46][47][48][49][50].…”

Tailoring of the chlorine sensing properties of substituted metal phthalocyanines non-covalently anchored on single-walled carbon nanotubes

“…Among the organic semiconductors, metallophthalocyanines (MPcs) are attractive choices for the noncovalent functionalization of CNTs because of the synergic interaction of MPcs with CNTs due to p-p interactions. 20,21 MPcs have emerged as outstanding sensing materials in highly selective, sensitive and reversible chemiresistive gas sensors to detect various toxic gases due to their conjugated macrocyclic units. 22,23 We have previously reported the nanostructured growth of substituted MPcs for ppb level Cl 2 gas sensors with detection limits as low as 5 ppb.…”