The aggregation of a free base porphyrin, meso-tetrakis(4-carboxyphenyl)porphyrin and its Zn(II) derivative have been studied at the air/water interface in the presence of a p-tert-butylcalyx[8]arene matrix. The mixed Langmuir films were obtained either by premixing the compounds (cospreading) or by sequential addition. The negative deviation from the additivity rule of the cospread films is indicative of a comparatively good miscibility that was further confirmed by Brewster angle microscopy. The images of the cospread mixed films showed a more homogeneous morphology in comparison with those of pure porphyrin that is attributed to a deeper and earlier self-aggregation state at the interface of the latter. These results were similar for both porphyrins and revealed the disaggregating effect of the calixarene matrix. The orientation and association of the porphyrins were studied by UV-visible reflection spectroscopy at the interface. A different aggregation behavior can be inferred from the resulting spectra, and a higher orientational freedom was observed when the molecules were less aggregated in mixed cospreaded films. The disaggregating effect was retained when the films were transferred to solid supports as demonstrated by UV-visible spectroscopy. Finally, the potential use of these Langmuir-Blodgett films as optical gas sensors was tested against ammonia and amine vapors. The changes in the spectrum in the presence of the volatile compounds are higher for the Zn-porphyrin. The presence of calixarene enhances the sensor response due to the higher accessibility of volatiles to disaggregated porphyrins in the mixed films. The resulting changes were mapped into a numerical matrix that can be transformed into a color pattern to easily discriminate among these gases.
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