Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications
Radicals based on arylamine cyclophanes can be used as functional materials and show application potential in fields such as synthetic chemistry, molecular electronic components, organic light-emitting diodes, and catalytic chemistry. Using a Buchwald–Hartwig palladium-catalyzed aryl halide aminatio...
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MDPI AG
2024-02-01
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| author | Shunjie Li Jian Chen |
| author_facet | Shunjie Li Jian Chen |
| author_sort | Shunjie Li |
| collection | DOAJ |
| description | Radicals based on arylamine cyclophanes can be used as functional materials and show application potential in fields such as synthetic chemistry, molecular electronic components, organic light-emitting diodes, and catalytic chemistry. Using a Buchwald–Hartwig palladium-catalyzed aryl halide amination method, we synthesized a series of neutral hexaazacyclophane compounds <b>1</b>–<b>3</b> with different substituents in the <i>meta–meta–meta</i> positions of the phenyl rings. Three characteristic high-spin hexaazacyclophane diradical dications were obtained by two-electron oxidation using AgSbF<sub>6</sub>: <b>1<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>, <b>2<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>, and <b>3<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>. The electronic structures and physical properties of these compounds were then investigated by <sup>1</sup>H and <sup>13</sup>C nuclear magnetic resonance spectroscopy, cyclic voltammetry, electron paramagnetic resonance spectroscopy, superconducting quantum interferometry, ultraviolet–visible spectroscopy, and density functional theory calculations. The findings provide new ideas for designing radical species with novel physical properties and electronic structures. Importantly, the obtained radical species are not sensitive to air, making them valuable functional materials for practical applications. |
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| format | Article |
| id | doaj.art-ecba56f921a14a539017cdf232fffa96 |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-07T22:20:22Z |
| publishDate | 2024-02-01 |
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| spelling | doaj.art-ecba56f921a14a539017cdf232fffa962024-02-23T15:28:53ZengMDPI AGMolecules1420-30492024-02-0129478910.3390/molecules29040789Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical DicationsShunjie Li0Jian Chen1College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, ChinaCollege of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, ChinaRadicals based on arylamine cyclophanes can be used as functional materials and show application potential in fields such as synthetic chemistry, molecular electronic components, organic light-emitting diodes, and catalytic chemistry. Using a Buchwald–Hartwig palladium-catalyzed aryl halide amination method, we synthesized a series of neutral hexaazacyclophane compounds <b>1</b>–<b>3</b> with different substituents in the <i>meta–meta–meta</i> positions of the phenyl rings. Three characteristic high-spin hexaazacyclophane diradical dications were obtained by two-electron oxidation using AgSbF<sub>6</sub>: <b>1<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>, <b>2<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>, and <b>3<sup>2·+</sup></b>•2[SbF<sub>6</sub>]<sup>−</sup>. The electronic structures and physical properties of these compounds were then investigated by <sup>1</sup>H and <sup>13</sup>C nuclear magnetic resonance spectroscopy, cyclic voltammetry, electron paramagnetic resonance spectroscopy, superconducting quantum interferometry, ultraviolet–visible spectroscopy, and density functional theory calculations. The findings provide new ideas for designing radical species with novel physical properties and electronic structures. Importantly, the obtained radical species are not sensitive to air, making them valuable functional materials for practical applications.https://www.mdpi.com/1420-3049/29/4/789triarylaminepyrenediradicalcationnitrogenpalladium-catalyzed |
| spellingShingle | Shunjie Li Jian Chen Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications Molecules triarylamine pyrene diradical cation nitrogen palladium-catalyzed |
| title | Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications |
| title_full | Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications |
| title_fullStr | Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications |
| title_full_unstemmed | Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications |
| title_short | Synthesis and Properties of Novel Alkyl-Substituted Hexaazacyclophanes and Their Diradical Dications |
| title_sort | synthesis and properties of novel alkyl substituted hexaazacyclophanes and their diradical dications |
| topic | triarylamine pyrene diradical cation nitrogen palladium-catalyzed |
| url | https://www.mdpi.com/1420-3049/29/4/789 |
| work_keys_str_mv | AT shunjieli synthesisandpropertiesofnovelalkylsubstitutedhexaazacyclophanesandtheirdiradicaldications AT jianchen synthesisandpropertiesofnovelalkylsubstitutedhexaazacyclophanesandtheirdiradicaldications |