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Redox-Associated Variation of Hückel Aromaticity from Lactam-Embedded Smallest Antiaromatic trans-Doubly N-Confused Porphyrins: Synthesis and Characterization.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-01-06 , DOI: 10.1021/acs.joc.9b02788 Nyancy Halder 1 , Mohandas Sangeetha 2 , Dandamudi Usharani 2, 3 , Harapriya Rath 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-01-06 , DOI: 10.1021/acs.joc.9b02788 Nyancy Halder 1 , Mohandas Sangeetha 2 , Dandamudi Usharani 2, 3 , Harapriya Rath 1
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High-yield synthesis, spectroscopic and solid-state structural proof of the lactam-embedded smallest ever metal-free stable Hückel antiaromatic trans-doubly N-confused [16] porphyrins are reported. These new facets of trans-doubly N-confused porphyrins have been anticipated to exhibit the redox-associated variation of Hückel aromaticity as a mere consequence of the amido-like structures of the N-confused N-methyl pyrrole rings of the macrocycles. Strong aromaticity upon NaBH4 reduction leading to a resonance dipolar structure of the [18]π-conjugated system as the reduced congener with concomitant Hückel topology are the important highlights. Excellent agreement between experimental spectroscopic measurements and the theoretically determined properties elucidate aromaticity switching upon chemical reduction. Recent years have witnessed an upsurge of demand for the experimental realization of stable antiaromatic systems because of their versatile applications in material science. The conformational rigidity and the enriched stability of these novel 16π antiaromatic doubly N-confused porphyrins might entitle these macrocycles toward such applications.
中文翻译：
内酰胺包埋的最小抗芳族反双N杂卟啉中Hückel芳香度的氧化还原相关变化：合成和表征。
据报道，内酰胺包埋的最小的无金属稳定的Hückel抗芳族反式双氮键[16]卟啉具有高产率的合成，光谱学和固态结构证明。预计这些新的反式双氮杂卟啉的新面将显示出Hückel芳香性的氧化还原相关变化，这仅仅是大环N混淆的N-甲基吡咯环的酰胺样结构的结果。重要的亮点是在NaBH4还原后具有[18]π-共轭体系共振偶极结构的强芳香性，这是伴随Hückel拓扑结构的还原同类物。实验光谱测量值和理论上确定的特性之间的极佳一致性阐明了化学还原后的芳香性转换。近年来，由于稳定的抗芳族体系在材料科学中的广泛应用，对稳定的抗芳族体系的实验实现的需求激增。这些新颖的16π抗芳香族双N杂卟啉的构象刚度和丰富的稳定性可能使这些大环化合物可以用于此类应用。
更新日期：2020-01-06
中文翻译：
内酰胺包埋的最小抗芳族反双N杂卟啉中Hückel芳香度的氧化还原相关变化：合成和表征。
据报道，内酰胺包埋的最小的无金属稳定的Hückel抗芳族反式双氮键[16]卟啉具有高产率的合成，光谱学和固态结构证明。预计这些新的反式双氮杂卟啉的新面将显示出Hückel芳香性的氧化还原相关变化，这仅仅是大环N混淆的N-甲基吡咯环的酰胺样结构的结果。重要的亮点是在NaBH4还原后具有[18]π-共轭体系共振偶极结构的强芳香性，这是伴随Hückel拓扑结构的还原同类物。实验光谱测量值和理论上确定的特性之间的极佳一致性阐明了化学还原后的芳香性转换。近年来，由于稳定的抗芳族体系在材料科学中的广泛应用，对稳定的抗芳族体系的实验实现的需求激增。这些新颖的16π抗芳香族双N杂卟啉的构象刚度和丰富的稳定性可能使这些大环化合物可以用于此类应用。
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