Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia
In this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR<sub>4</sub>-np, R = F, Cl) and peripheral (ZnPcR<sub>4</sub>-p, R = F, Cl) positions of macrocycle, on their structure and chemir...
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| Format: | Article |
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MDPI AG
2021-06-01
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| Series: | Chemosensors |
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| Online Access: | https://www.mdpi.com/2227-9040/9/6/137 |
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| author | Dmitry Bonegardt Darya Klyamer Aleksandr Sukhikh Pavel Krasnov Pavel Popovetskiy Tamara Basova |
| author_facet | Dmitry Bonegardt Darya Klyamer Aleksandr Sukhikh Pavel Krasnov Pavel Popovetskiy Tamara Basova |
| author_sort | Dmitry Bonegardt |
| collection | DOAJ |
| description | In this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR<sub>4</sub>-np, R = F, Cl) and peripheral (ZnPcR<sub>4</sub>-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 (ZnPcR<sub>4</sub>) 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 ZnPcHal<sub>4</sub> 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 ZnPcCl<sub>4</sub>-np < ZnPcF<sub>4</sub>-np < ZnPcF<sub>4</sub>-p < ZnPcCl<sub>4</sub>-p, which is in good agreement with the values of bonding energy between hydrogen atoms of NH<sub>3</sub> and halogen substituents in the phthalocyanine rings. ZnPcCl<sub>4</sub>-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 ZnPcF<sub>4</sub>-p films. It was shown that both ZnPcF<sub>4</sub>-p and ZnPcCl<sub>4</sub>-p and can be used for the selective detection of NH<sub>3</sub> in the presence of carbon dioxide, dichloromethane, acetone, toluene, and ethanol. |
| first_indexed | 2024-03-10T10:29:33Z |
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| institution | Directory Open Access Journal |
| issn | 2227-9040 |
| language | English |
| last_indexed | 2024-03-10T10:29:33Z |
| publishDate | 2021-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Chemosensors |
| spelling | doaj.art-b377b4b4ff2943ee89dd9f87646183ca2023-11-21T23:48:02ZengMDPI AGChemosensors2227-90402021-06-019613710.3390/chemosensors9060137Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to AmmoniaDmitry Bonegardt0Darya Klyamer1Aleksandr Sukhikh2Pavel Krasnov3Pavel Popovetskiy4Tamara Basova5Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaInternational Research Center of Spectroscopy and Quantum Chemistry, Siberian Federal University, 660074 Krasnoyarsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaNikolaev Institute of Inorganic Chemistry SB RAS, 3 Lavrentiev Pr., 630090 Novosibirsk, RussiaIn this work, the effect of fluorine and chlorine substituents in tetrasubstituted zinc phthalocyanines, introduced into the non-peripheral (ZnPcR<sub>4</sub>-np, R = F, Cl) and peripheral (ZnPcR<sub>4</sub>-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 (ZnPcR<sub>4</sub>) 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 ZnPcHal<sub>4</sub> 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 ZnPcCl<sub>4</sub>-np < ZnPcF<sub>4</sub>-np < ZnPcF<sub>4</sub>-p < ZnPcCl<sub>4</sub>-p, which is in good agreement with the values of bonding energy between hydrogen atoms of NH<sub>3</sub> and halogen substituents in the phthalocyanine rings. ZnPcCl<sub>4</sub>-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 ZnPcF<sub>4</sub>-p films. It was shown that both ZnPcF<sub>4</sub>-p and ZnPcCl<sub>4</sub>-p and can be used for the selective detection of NH<sub>3</sub> in the presence of carbon dioxide, dichloromethane, acetone, toluene, and ethanol.https://www.mdpi.com/2227-9040/9/6/137metal phthalocyanineschemiresistive sensorsgas sensorsthin filmsammonia halogen substituentscrystal structure |
| spellingShingle | Dmitry Bonegardt Darya Klyamer Aleksandr Sukhikh Pavel Krasnov Pavel Popovetskiy Tamara Basova Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia Chemosensors metal phthalocyanines chemiresistive sensors gas sensors thin films ammonia halogen substituents crystal structure |
| title | Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia |
| title_full | Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia |
| title_fullStr | Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia |
| title_full_unstemmed | Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia |
| title_short | Fluorination vs. Chlorination: Effect on the Sensor Response of Tetrasubstituted Zinc Phthalocyanine Films to Ammonia |
| title_sort | fluorination vs chlorination effect on the sensor response of tetrasubstituted zinc phthalocyanine films to ammonia |
| topic | metal phthalocyanines chemiresistive sensors gas sensors thin films ammonia halogen substituents crystal structure |
| url | https://www.mdpi.com/2227-9040/9/6/137 |
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