Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity via cross-coupling reactions.
Functionalisation of conjugated macrocycles with type I and II concealed antiaromaticity via cross-coupling reactions.
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DOI：
10.1039/d3me00045a
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发表时间：
2023-06-06
影响因子：
3.6
通讯作者：
中科院分区：
文献类型：
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作者：
共轭大环可以表现出隐藏的反芳香性;也就是说，尽管不是反芳香性的，但在特定情况下，它们可以表现出通常在反芳香分子中观察到的性质，这是由于它们的形式大环4 n π-电子系统。对环芳四烯（PCT）及其衍生物是表现出这种行为的大环化合物的主要实例。在氧化还原反应和光激发时，它们表现得像反芳香分子（分别需要I型和II型隐藏的反芳香性），这种现象显示出在电池电极材料和其他电子应用中的潜力。然而，由于缺乏卤化分子结构单元，使得PCTs通过交叉偶联反应整合到更大的共轭分子中，从而阻碍了对PCTs的进一步探索。在这里，我们提出了两个二溴化的PCTs，从一个三步合成的区域异构体的混合物，并证明其功能化通过铃木交叉偶联反应。光学、电化学和理论研究表明，芳基取代基可以巧妙地调节PCT的性质和行为，这表明这是进一步探索这类有前途的材料的可行策略。介绍了卤代对环芳四烯（PCT），用于通过交叉偶联反应将PCT基序整合到更大的共轭分子中。
Conjugated macrocycles can exhibit concealed antiaromaticity; that is, despite not being antiaromatic, under specific circumstances, they can display properties typically observed in antiaromatic molecules due to their formal macrocyclic 4n π-electron system. Paracyclophanetetraene (PCT) and its derivatives are prime examples of macrocycles exhibiting this behaviour. In redox reactions and upon photoexcitation, they have been shown to behave like antiaromatic molecules (requiring type I and II concealed antiaromaticity, respectively), with such phenomena showing potential for use in battery electrode materials and other electronic applications. However, further exploration of PCTs has been hindered by the lack of halogenated molecular building blocks that would permit their integration into larger conjugated molecules by cross-coupling reactions. Here, we present two dibrominated PCTs, obtained as a mixture of regioisomers from a three-step synthesis, and demonstrate their functionalisation via Suzuki cross-coupling reactions. Optical, electrochemical, and theoretical studies reveal that aryl substituents can subtly tune the properties and behaviour of PCT, showing that this is a viable strategy in further exploring this promising class of materials. Halogenated paracyclophanetetraenes (PCTs) for the integration of the PCT motif into larger conjugated molecules by cross-coupling reactions are introduced.
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影响因子：
2.8
作者：
Plasser F;Glöcklhofer F
通讯作者：
Glöcklhofer F
影响因子：
15
作者：
El Bakouri, Ouissam;Smith, Joshua R.;Ottosson, Henrik
通讯作者：
Ottosson, Henrik
DOI：
10.3891/acta.chem.scand.37b-0589
发表时间：
1983-01-01
期刊：
ACTA CHEMICA SCANDINAVICA SERIES B-ORGANIC CHEMISTRY AND BIOCHEMISTRY
影响因子：
--
作者：
THULIN, B;WENNERSTROM, O
通讯作者：
WENNERSTROM, O
DOI：
10.3891/acta.chem.scand.31b-0135
发表时间：
1977-01-01
期刊：
ACTA CHEMICA SCANDINAVICA SERIES B-ORGANIC CHEMISTRY AND BIOCHEMISTRY
影响因子：
--
作者：
THULIN, B;WENNERSTROM, O;CHMIELARZ, B
通讯作者：
CHMIELARZ, B
影响因子：
16.6
作者：
Eder, Simon;Ding, Bowen;Thornton, Daisy B.;Sammut, Darlene;White, Andrew J. P.;Plasser, Felix;Stephens, Ifan E. L.;Heeney, Martin;Mezzavilla, Stefano;Glocklhofer, Florian
通讯作者：
Glocklhofer, Florian