Assisted formation of chiral porphyrin homoaggregates by an induced helical poly(phenylacetylene) template and their chiral memory.
Assisted formation of chiral porphyrin homoaggregates by an induced helical poly(phenylacetylene) template and their chiral memory.
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DOI：
10.1002/anie.200504162
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发表时间：
2006-04
影响因子：
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通讯作者：
H. Onouchi;Toyoharu Miyagawa;K. Morino;E. Yashima
中科院分区：
文献类型：
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作者：
H. Onouchi;Toyoharu Miyagawa;K. Morino;E. Yashima
近年来，非手性发色团，特别是卟啉和菁染料自组装成具有可控螺旋意义的超分子螺旋J-聚集体引起了人们的极大兴趣，因为它在光电子材料[3]和光合作用模型中具有潜在的应用。[4]手性小分子[1e-g，i]和生物聚合物[1a-d，f，h，j]经常被用作诱导手性的模板。物理作用力，如选择的旋涡搅拌或旋转，也可以诱导手性J聚集的手性偏置。[2]以前，我们报道了带正电的动态外消旋螺旋聚乙炔，聚(4-(N，N-二异丙氨基甲基)苯乙炔)(聚-1-HCl；图1)的盐酸盐，当在水中被少量手性酸诱导时，通过离子相互作用形成过量的螺旋感1。我们现在发现，聚-1-HCl可以将疏水的手性客体(S)-1，1‘-双-2-萘酚(2)捕获到它在水中的疏水空腔中，这导致了由于大的手性放大而导致的以单手螺旋为主的ICD。诱导的螺旋在聚合物表面具有带电的侧基，这些基团以螺旋阵列的形式排列，具有一个主要的螺旋感受器，这可以用作具有相反电荷的无手性卟啉的进一步超分子螺旋阵列的模板，例如
The self-assembly of achiral chromophores, in particular, porphyrins and cyanine dyes, into supramolecular helical J-aggregates with a controlled helix sense [1, 2] has attracted significant interest in recent years because of its potential application to optoelectronic materials [3] as well as models for photosynthesis.[4] Chiral small molecules [1e–g, i] and biopolymers [1a–d, f, h, j] have often been used as templates for the induction of chirality. Physical forces, such as selected vortex stirring or spinning, can also induce a chiral bias to such a chiral J-aggregation.[2] Previously, we reported that a positively charged, dynamically racemic helical polyacetylene, the hydrochloride salt of poly (4-(N, N-diisopropylaminomethyl) phenylacetylene)(poly-1-HCl; Figure 1), formed an excess helical sense of one through ionic interactions in water when induced by a small amount of chiral acids.[5] The polymer backbone region of the complexes exhibited a characteristic induced circular dichroism (ICD). We now find that poly-1-HCl can trap a hydrophobic chiral guest,(S)-1, 1’-bi-2-naphthol (2), within its hydrophobic cavity in water which results in an intense ICD owing to a predominantly one-handed helix as a consequence of a large chiral amplification. The induced helix possesses charged pendant groups at the polymer surface which arrange in a helical array with one predominant screw sense, which can serve as the template for further supramolecular helical arrays of an achiral porphyrin with opposite charges, such