Thin Films of Chlorinated Vanadyl Phthalocyanines as Active Layers of Chemiresistive Sensors for the Detection of Ammonia.

Halogenated metal phthalocyanines are promising materials for the manufacture of active layers of chemiresistive sensors for the detection of various gases. Despite the high interest in such sensors, there are few systematic studies of the position of halogen substituents in phthalocyanine macroring on the chemiresistive response of their films to gases. In this work, we prepared and studied films of novel tetrachlorosubstituted vanadyl phthalocyanine derivatives with Cl substituents in the peripheral (VOPcCl4-p) and nonperipheral (VOPcCl4-np) positions of the phthalocyanine ring as active layers of chemiresistive sensors to reveal the effect of the position of substituents on their structure and sensor response to low concentrations of NH3. It was shown that the films of VOPcCl4-p exhibited a noticeably higher sensor response to NH3 than the VOPcCl4-np ones. The limit of detection of NH3 was 0.7 ppm. The sensing layers demonstrated a reversible sensor response at room temperature with fairly low response/recovery times. It was also demonstrated that NH3 can be detected in the presence of various interfering gases (CO2 and H2) and some volatile organic vapors, as well as in a mixture of gases with a composition close to exhaled air.

Octafluoro-Substituted Phthalocyanines of Zinc, Cobalt, and Vanadyl: Single Crystal Structure, Spectral Study and Oriented Thin Films.

In this work, octafluoro-substituted phthalocyanines of zinc, vanadyl, and cobalt (MPcF8, M = Zn(II), Co(II), VO) were synthesized and studied. The structures of single crystals of the obtained phthalocyanines were determined. To visualize and compare intermolecular contacts in MPcF8, an analysis of Hirshfeld surfaces (HS) was performed. MPcF8 nanoscale thickness films were deposited by organic molecular beam deposition technique and their structure and orientation were studied using X-ray diffraction. Comparison of X-ray diffraction patterns of thin films with the calculated diffractograms showed that all three films consisted of a single crystal phase, which corresponded to a phase of single crystals. Only one strong diffraction peak corresponding to the plane (001) was observed on the diffraction pattern of each film, which indicated a strong preferred orientation with the vast majority of crystallites oriented with a (001) crystallographic plane parallel to the substrate surface. The effect of the central metals on the electronic absorption and vibrational spectra of the studied phthalocyanines as well as on the electrical conductivity of their films is also discussed.

Chlorosubstituted Copper Phthalocyanines: Spectral Study and Structure of Thin Films.

In this work, the tetra-, octa- and hexadecachloro-substituted copper phthalocyanines CuPcClx (where x can equal 4, 8 or 16) were investigated by the methods of vibrational (IR and Raman) spectroscopy and X-ray diffraction. The assignment of the most intense bands, both in IR and Raman spectra, was carried out on the basis of DFT calculations. The structure of a CuPcCl4 single crystal grown by sublimation in vacuum was refined for the first time. The effect of chloro-substitution on the structure of CuPcClx thin films deposited in a vacuum onto a glass substrate at 50 and 200 °C was studied. It was shown that CuPcCl4 formed polycrystalline films with the preferential orientation of the (100) crystallographic plane of crystallites parallel to the substrate surface when deposited on a substrate at 50 °C. Introduction of more Cl-substituents into the phthalocyanine macrocycle leads to the formation of amorphous films on the substrates at 50 °C. At the elevated substrate temperature, the growth of polycrystalline disordered films was observed for all three copper phthalocyanines.