Helicity Induction on Poly(phenylacetylene)s Bearing Phosphonic Acid Pendants with Chiral Amines and Memory of the Macromolecular Helicity Assisted by Interaction with Achiral Amines in Dimethyl Sulfoxide
Helicity Induction on Poly(phenylacetylene)s Bearing Phosphonic Acid Pendants with Chiral Amines and Memory of the Macromolecular Helicity Assisted by Interaction with Achiral Amines in Dimethyl Sulfoxide
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DOI：
10.1021/ma049066v
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发表时间：
2004-06
期刊：
影响因子：
5.5
通讯作者：
H. Onouchi;Daisuke Kashiwagi;K. Hayashi;Katsuhiro Maeda;E. Yashima
中科院分区：
文献类型：
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作者：
H. Onouchi;Daisuke Kashiwagi;K. Hayashi;Katsuhiro Maeda;E. Yashima
通过（4-乙炔基苯基）膦酸二乙酯的聚合、二乙酯基团的水解和（4-乙炔基苯基）膦酸乙酯的聚合，分别合成了两种新型的带有膦酸残基（poly-1）和膦酸单乙酯（poly-2）的有规立构聚苯乙炔。发现聚合物在二甲亚砜（DMSO）中通过非共价酸碱相互作用与各种手性胺络合后形成主要的单手螺旋构象。复合物在聚合物主链的UV-可见光区表现出诱导圆二色性（ICD）。特别地，聚-2是诱导的螺旋聚合物，其对胺的手性比聚-1和聚（（4-羧基苯基）乙炔）更敏感，并且当与具有相同绝对构型的手性胺络合时产生相同的科顿效应符号。此外，手性胺诱导的poly-1和poly-2的大分子螺旋度在手性胺作用后被“记忆”。
Two novel stereoregular poly(phenylacetylene)s bearing a phosphonic acid residue (poly-1) and its monoethyl ester (poly-2) as pendants were prepared by the polymerization of diethyl (4-ethynylphenyl)phosphonate followed by hydrolysis of the diethyl ester groups and polymerization of ethyl (4-ethynylphenyl)phosphonate, respectively. The polymers were found to form a predominantly one-handed helical conformation upon complexation with various chiral amines through noncovalent acid−base interactions in dimethyl sulfoxide (DMSO). The complexes exhibited an induced circular dichroism (ICD) in the UV−visible region of the polymer backbones. In particular, poly-2 is an induced helical polymer more sensitive to the chirality of amines than poly-1 and poly((4-carboxyphenyl)acetylene) and yields the same Cotton effect sign when complexed with chiral amines of the same absolute configuration. Moreover, the macromolecular helicity of poly-1 and poly-2 induced by chiral amines was “memorized” after the chiral amines w...