A comparative analysis of the chemiresistive sensor response of thin films of a series of tetrasubstituted phthalocyanines of various metals with F-substituent in peripheral (MPcF4-p, M = Cu, Co, Zn, Pb, VO) and non-peripheral (MPcF4-np) positions in macroring to low concentrations of ammonia (1–50 ppm) was carried out. It was found that MPcF4-p films exhibit a higher sensor response than MPcF4-np ones. A CoPcF4-p film demonstrated a calculated LOD of 0.01 ppm with a recovery time of 215 s, while a VOPcF4-p film had LOD of 0.04 ppm and the recovery time of 270 s. The selectivity test showed that CO2, ethanol, acetone, benzene, and formaldehyde did not interfere with the determination of ammonia, while H2S at a concentration of more than 10 ppm could act as an interfering gas. It was shown that, as a result of quantum-chemical calculations, the observed regularities are best described by the interaction of NH3 with phthalocyanines through the formation of hydrogen bonds between NH3 and side atoms of the macroring. In the case of MPcF4-p, the NH3 molecule approaches the macrocycle more closely and binds more strongly than in the case of MPcF4-np. The stronger binding leads to a stronger effect of the ammonia molecule on the electronic structure of phthalocyanine and, as a consequence, on the chemiresistive sensor response of the films to ammonia.

In this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR4-np, R = F, Cl) and peripheral (ZnPcR4-p, R = F, Cl) positions of macrocycle, on their structure and chemiresistive sensor response to low concentration of ammonia is studied. The structure and morphology of the zinc phthalocyanines films (ZnPcR4) were investigated by X-ray diffraction and atomic force microscopy methods. To understand different effects of chlorine and fluorine substituents, the strength and nature of the bonding of ammonia and ZnPcHal4 molecules were studied by quantum chemical simulation. It was shown on the basis of comparative analysis that the sensor response to ammonia was found to increase in the order ZnPcCl4-np < ZnPcF4-np < ZnPcF4-p < ZnPcCl4-p, which is in good agreement with the values of bonding energy between hydrogen atoms of NH3 and halogen substituents in the phthalocyanine rings. ZnPcCl4-p films demonstrate the maximal sensor response to ammonia with the calculated detection limit of 0.01 ppm; however, they are more sensitive to humidity than ZnPcF4-p films. It was shown that both ZnPcF4-p and ZnPcCl4-p and can be used for the selective detection of NH3 in the presence of carbon dioxide, dichloromethane, acetone, toluene, and ethanol.

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.