Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects
The application of DFT computational method (B3LYP/6-311++G(d,p)) to mono- and poly(CF<sub>3</sub>)substituted naphthalene derivatives helps to study changes in the electronic properties of these compounds under the influence of 11 substituents (-Br, -CF<sub>3</sub>, -CH<s...
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| Format: | Article |
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MDPI AG
2022-06-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/13/4173 |
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| author | Adam Sokół Henryk Koroniak Marcin Hoffmann Tomasz Siodła |
| author_facet | Adam Sokół Henryk Koroniak Marcin Hoffmann Tomasz Siodła |
| author_sort | Adam Sokół |
| collection | DOAJ |
| description | The application of DFT computational method (B3LYP/6-311++G(d,p)) to mono- and poly(CF<sub>3</sub>)substituted naphthalene derivatives helps to study changes in the electronic properties of these compounds under the influence of 11 substituents (-Br, -CF<sub>3</sub>, -CH<sub>3</sub>, -CHO, -Cl, -CN, -F, -NH<sub>2</sub>, -NMe<sub>2</sub>, -NO<sub>2</sub>, and -OH) to confront substituent effects in naphthalene with an analogous situation in benzene. This paper shows the dependencies of theoretically calculated SESE (Substituent Effect Stabilization Energy) values on empirically determined, well-defined Hammett-type constants (<i>σ<sub>p</sub></i>, <i>σ<sub>m</sub></i>, <i>R</i>, and <i>F</i>). Described poly(CF<sub>3</sub>)substituted derivatives of naphthalene are, so far, the most sensitive molecular probes for the substituent effects in the aromatic system. The presence of the trifluoromethyl groups of such an expressive nature significantly increases the sensitivity of the SESE to changes caused by another substitution. Further, the more -CF<sub>3</sub> groups are attached to the naphthalene ring, the more sensitive the probe is. Certain groups of probes show additivity of sensitivity: the obtained sensitivity relates to the sum of the sensitivities of the mono(CF<sub>3</sub>)substituted probes. |
| first_indexed | 2024-03-09T12:44:03Z |
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| id | doaj.art-9c005614bee94c3a932b6e919d3142b4 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T12:44:03Z |
| publishDate | 2022-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-9c005614bee94c3a932b6e919d3142b42023-11-30T22:14:39ZengMDPI AGMolecules1420-30492022-06-012713417310.3390/molecules27134173Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent EffectsAdam Sokół0Henryk Koroniak1Marcin Hoffmann2Tomasz Siodła3Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznan, PolandFaculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznan, PolandFaculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznan, PolandFaculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznan, PolandThe application of DFT computational method (B3LYP/6-311++G(d,p)) to mono- and poly(CF<sub>3</sub>)substituted naphthalene derivatives helps to study changes in the electronic properties of these compounds under the influence of 11 substituents (-Br, -CF<sub>3</sub>, -CH<sub>3</sub>, -CHO, -Cl, -CN, -F, -NH<sub>2</sub>, -NMe<sub>2</sub>, -NO<sub>2</sub>, and -OH) to confront substituent effects in naphthalene with an analogous situation in benzene. This paper shows the dependencies of theoretically calculated SESE (Substituent Effect Stabilization Energy) values on empirically determined, well-defined Hammett-type constants (<i>σ<sub>p</sub></i>, <i>σ<sub>m</sub></i>, <i>R</i>, and <i>F</i>). Described poly(CF<sub>3</sub>)substituted derivatives of naphthalene are, so far, the most sensitive molecular probes for the substituent effects in the aromatic system. The presence of the trifluoromethyl groups of such an expressive nature significantly increases the sensitivity of the SESE to changes caused by another substitution. Further, the more -CF<sub>3</sub> groups are attached to the naphthalene ring, the more sensitive the probe is. Certain groups of probes show additivity of sensitivity: the obtained sensitivity relates to the sum of the sensitivities of the mono(CF<sub>3</sub>)substituted probes.https://www.mdpi.com/1420-3049/27/13/4173naphthalenesubstituent effectdensity functional theory (DFT)substituent effect stabilization energy (SESE)trifluoromethyl group |
| spellingShingle | Adam Sokół Henryk Koroniak Marcin Hoffmann Tomasz Siodła Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects Molecules naphthalene substituent effect density functional theory (DFT) substituent effect stabilization energy (SESE) trifluoromethyl group |
| title | Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects |
| title_full | Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects |
| title_fullStr | Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects |
| title_full_unstemmed | Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects |
| title_short | Naphthalene vs. Benzene as a Transmitting Moiety: Towards the More Sensitive Trifluoromethylated Molecular Probes for the Substituent Effects |
| title_sort | naphthalene vs benzene as a transmitting moiety towards the more sensitive trifluoromethylated molecular probes for the substituent effects |
| topic | naphthalene substituent effect density functional theory (DFT) substituent effect stabilization energy (SESE) trifluoromethyl group |
| url | https://www.mdpi.com/1420-3049/27/13/4173 |
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