Self-Assembling Decacyclene Triimides Prepared through a Regioselective Hextuple Friedel-Crafts Carbamylation
Self-Assembling Decacyclene Triimides Prepared through a Regioselective Hextuple Friedel-Crafts Carbamylation
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DOI：
10.1002/anie.201207608
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发表时间：
2013-01-01
影响因子：
16.6
通讯作者：
Wudl, Fred
中科院分区：
文献类型：
--
作者：
Pho, Toan V.;Toma, Francesca M.;Wudl, Fred
有机半导体已成为追求下一代柔性电子器件（如有机光致发光器件和有机发光二极管）的成本效益生产中不可或缺的组成部分。[1]尽管最初关注其功效，但p型（空穴传输）有机半导体的性能已经稳步提高到证明电荷载流子迁移率超过非晶硅的程度。[2]虽然这些p型材料的性能通常超过了它们的n型（电子传输）对应物，但n型半导体在应用中是必不可少的，例如互补电路[3]和有机光致发光。[4]然而，n型材料的制备受到有机阴离子在氧化气氛中的固有不稳定性和未取代的芳烃/杂芳烃的固有低电子亲和力的阻碍。[5]为了生产具有增加的电子亲合性的n型材料，最直接的方法涉及将缺电子基团连接到π-共轭核上，并且实际上，萘嵌苯的二酰亚胺如萘和二萘嵌苯包括研究最充分的n型有机半导体类别之一。[6]由于萘嵌苯二酰亚胺含有两个缺电子的酰亚胺基团，赋予n型字符，否则p型多环烃，我们把我们的注意力集中在一个核心结构，可以支持两个以上的酰亚胺取代基。多个酰亚胺取代基可以增加母体材料的电子亲和力，从而促进电子注入和电荷传输。然而，引入多个酰亚胺基团是一个合成挑战，只有少数三酰亚胺和四酰亚胺的例子是通过冗长和/或低产率的合成路线制备的-通过对萘嵌苯的氧化Diels-Alder反应[7]或萘嵌苯二酰亚胺的赤道融合。[8]在此，我们提供了一种简单有效的途径，得到由多环烃十环烯（decacyclene）支撑的新型三酰亚胺（1，方案1），这导致了一类有前途的n型有机半导体。十环烯是一种商业上可获得的具有三重对称性的10环稠合多环烃，首次报道于20世纪之交。从苊的氧化环三聚反应中一步产生，decacyclene先前已经探索了其可逆地接受多达四个电子的能力。[10]尽管如此，尽管这种令人印象深刻的电化学，十环烯衍生物的n型性质只研究过一次，[11]更多的注意力集中在其在自由基阳离子盐中的供电子特性上。[12]十环烯的一个值得注意的特征是其固有的支持多个官能团的潜力。比如说，
Organic semiconductors have become indispensable building blocks in the quest for cost-effective production of nextgeneration flexible electronic devices such as organic photovoltaics and organic light-emitting diodes.[1] Despite initial concerns regarding their efficacy, the performance of p-type (hole-transporting) organic semiconductors has steadily improved to the extent of demonstrating charge carrier mobilities exceeding that of amorphous silicon.[2] Although the performance of these p-type materials has typically exceeded that of their n-type (electron-transporting) counterparts, n-type semiconductors are essential in applications, such as complementary circuits [3] and organic photovoltaics.[4] The preparation of n-type materials, however, is hampered by the intrinsic instability of organic anions in an oxidative atmosphere and the inherently low electron affinities of unsubstituted arenes/heteroarenes.[5] To produce n-type materials with increased electron affinities, the most straightforward approach involves the attachment of electron-deficient groups onto a π-conjugated core, and indeed, the diimides of rylenes such as naphthalene and perylene comprise one of the most well-studied classes of n-type organic semiconductors.[6] Since the rylene diimides contain two electron-deficient imide groups that impart n-type character to an otherwise ptype polycyclic hydrocarbon, we focused our attention on a core structure that can support more than two imide substituents. Multiple imide substituents may increase the electron affinity of the parent material, thereby facilitating electron injection, and charge transport. However, the incorporation of multiple imide groups is a synthetic challenge, and only a few examples of tri-and tetraimides have been prepared through lengthy and/or low-yielding synthetic routes—either through oxidative Diels–Alder reactions on rylenes [7] or equatorial fusion of rylene diimides.[8] Herein, we provide a facile and efficient pathway towards novel triimides supported by the polycyclic hydrocarbon decacyclene (1, Scheme 1) that results in a promising class of n-type organic semiconductors.First reported at the turn of the 20th century,[9] decacyclene is a commercially available 10-ring fused polycyclic hydrocarbon with three-fold symmetry. Produced in one step from the oxidative cyclotrimerization of acenaphthene, decacyclene has been previously explored for its ability to reversibly accept up to four electrons.[10] Nevertheless, in spite of this impressive electrochemistry, the n-type properties of decacyclene derivatives have only been studied once,[11] with more attention being directed to its electron-donating character in radical cation salts.[12] A noteworthy feature of decacyclene is its inherent potential to support multiple functional groups. For instance,