Specific Interaction between Chloroform and the Pockets of Triangular Annulene Derivatives Providing Symmetry Carry-Over Crystallization
Specific Interaction between Chloroform and the Pockets of Triangular Annulene Derivatives Providing Symmetry Carry-Over Crystallization
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DOI：
10.1002/chem.200901848
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发表时间：
2009-01-01
影响因子：
4.3
通讯作者：
Miyata, Mikiji
中科院分区：
文献类型：
--
作者：
Hisaki, Ichiro;Senga, Hirofumi;Miyata, Mikiji
六氢三苯并[12]轮烯衍生物（DBA）[1]是具有以下结构特征的分子：1）共轭环上的离域π电子云和2）明确定义的三角形几何结构。[2]由于这些方面，DBA最近已经从光电材料[3]和超分子组装体的构建块等观点进行了研究。[4]DBA也是晶体超结构的有吸引力的构建块。[5]在这种情况下，我们设计了C3-对称DBA 1和2，以及3作为对照（图1a），因为1和2预计将通过供电子取代基和作为受体的芳族氢原子之间的弱氢键进行对称携带结晶（SCC）[6]（图1b）。此外，DBA的旋转灵活的取代基可以微调特殊的非符合时，分子被包装到晶体中。在对DBA的晶体工程的这项研究中，我们意外地在1和2的晶体中发现了DBA与氯仿的奇异络合物（图1c）。在配合物中，氯仿中的一个氢原子嵌入了DBA的“口袋”中，周围环绕着π电子，这实际上是DBA除了上述两种结构特征之外的另一种结构特征。这种DBA与中性分子的络合物迄今为止是未知的，尽管Youngs和同事报道了使用口袋的DBA的优异的有机金属络合物。[7]此外，络合作用似乎在本系统中对SCC起重要作用。[8]也就是说，氯仿帮助DBA形成具有C3对称内含物的2D层状网络[a] Dr. I. Hisaki，H. Senga，Y.坂本博士Tohnai，Prof. Dr. M.宫田
Hexadehydrotribenzo [12] annulene derivatives (DBAs)[1] are molecules that have the following structural characteristics: 1) delocalized π-electron clouds on the conjugated cycle and 2) a well-defined triangle geometry.[2] Because of these aspects, DBAs have been recently investigated from such viewpoints as optoelectronic materials [3] and building blocks for supramolecular assemblies.[4] DBAs are also attractive building blocks for crystalline superstructures.[5] In this context, we designed C3-symmetric DBAs 1 and 2, as well as 3 for a control (Figure 1a), because 1 and 2 are expected to undergo symmetry carry-over crystallization (SCC)[6] through weak hydrogen bonds between the electron-donating substituents and aromatic hydrogen atoms as acceptors (Figure 1b). Furthermore, the rotationally flexible substituents of the DBAs can fine-tune special noncoincidence when the molecules are packed into the crystals. During this study on crystal engineering of the DBAs, we serendipitously found exotic complexes of the DBAs with chloroform in crystals of 1 and 2 (Figure 1c). In the complexes, a hydrogen atom of the chloroform fits into the DBA s “pocket” surrounded by π electrons, which is actually another structural feature of the DBAs in addition to the two mentioned above. Such a complex of DBA with a neutral molecule has been hitherto unknown, although excellent organometallic complexes of DBAs using the pocket were reported by Youngs and co-workers.[7] Furthermore, the complexation seems to play a significant role for SCC in the present system.[8] Namely, chloroform assists the DBAs to form 2D layered networks with C3-symmetric inclusion [a] Dr. I. Hisaki, H. Senga, Y. Sakamoto, Dr. N. Tohnai, Prof. Dr. M. Miyata