Engineering double to quintuple stacks of a polarized aromatic in confined cavities.
Engineering double to quintuple stacks of a polarized aromatic in confined cavities.
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DOI：
10.1021/ja904063r
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发表时间：
2010-01
影响因子：
15
通讯作者：
Y. Yamauchi;M. Yoshizawa;M. Akita;M. Fujita
中科院分区：
文献类型：
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作者：
Y. Yamauchi;M. Yoshizawa;M. Akita;M. Fujita
离散的、明确的极性芳香芘-4,5-二酮(1)堆叠在有机柱状配位笼(2)的空腔中。堆积客体的数量(n)取决于柱的长度，当加入长（16.5 A）有机柱配体时，最多可观察到五层堆叠（n = 5）。正如之前报道的那样，吡啶-4,5-二酮(1)在固体状态下组装成无限柱状堆叠，但目前的工作表明，极化1即使在没有晶体填充效应的情况下也有很强的堆叠倾向。对于n = 2和3的结构，晶体学研究表明，1通过π - π相互作用在腔中堆叠，从而抵消了净偶极矩。这些结果强调了偶极-偶极相互作用以及pi-堆叠相互作用在1的柱状堆叠形成中的重要作用。
Discrete, well-defined stacks of the polarized aromatic pyrene-4,5-dione (1) were assembled in the cavities of organic-pillared coordination cages (2). The number (n) of stacked guests depends on the pillar length, and up to quintuple stacks (n = 5) were observed when long (16.5 A) organic pillar ligands were incorporated. As previously reported, pyrene-4,5-dione (1) assembles into infinite columnar stacks in the solid state, but the present work demonstrates that the polarized 1 has a strong propensity to stack in layers even in the absence of crystal packing effects. For n = 2 and 3 structures, crystallographic studies revealed that 1 stacks by pi-pi interactions in the cavity in such a way that a net dipole moment is canceled. These results emphasize the important role of dipole-dipole interactions as well as pi-stacking interactions in the formation of columnar stacks of 1.