Li Shunjie, Chen Jian
College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000, China.
College of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, China.
Molecules. 2024 Feb 8;29(4):789. doi: 10.3390/molecules29040789.
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 - with different substituents in the positions of the phenyl rings. Three characteristic high-spin hexaazacyclophane diradical dications were obtained by two-electron oxidation using AgSbF: •2[SbF], •2[SbF], and •2[SbF]. The electronic structures and physical properties of these compounds were then investigated by H and 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.
基于芳胺环番的自由基可作为功能材料，在合成化学、分子电子元件、有机发光二极管和催化化学等领域显示出应用潜力。我们采用布赫瓦尔德-哈特维希钯催化芳基卤胺化方法，合成了一系列在苯环位置具有不同取代基的中性六氮杂环番化合物。通过使用AgSbF₆进行双电子氧化，得到了三种具有代表性的高自旋六氮杂环番双自由基双阳离子：•₂[SbF₆]、•₂[SbF₆]和•₂[SbF₆]。然后通过¹H和¹³C核磁共振光谱、循环伏安法、电子顺磁共振光谱、超导量子干涉测量、紫外可见光谱以及密度泛函理论计算对这些化合物的电子结构和物理性质进行了研究。这些发现为设计具有新颖物理性质和电子结构的自由基物种提供了新思路。重要的是，所获得的自由基物种对空气不敏感，使其成为具有实际应用价值的功能材料。
