Tetrafluorosubstituted Metal Phthalocyanines: Study of the Effect of the Position of Fluorine Substituents on the Chemiresistive Sensor Response to Ammonia

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.