Syntheses and Chiroptical Properties of Optically Active Helical Poly(phenylacetylene)s Bearing [60]Fullerene Pendants
Syntheses and Chiroptical Properties of Optically Active Helical Poly(phenylacetylene)s Bearing [60]Fullerene Pendants
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DOI：
10.1021/ma7022342
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发表时间：
2007-11
期刊：
影响因子：
5.5
通讯作者：
Sousuke Ohsawa;Katsuhiro Maeda;E. Yashima
中科院分区：
文献类型：
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作者：
Sousuke Ohsawa;Katsuhiro Maeda;E. Yashima
在多聚甲醛和双十五烷基酮存在下，C_（60）分别与（R）-N-[1-（4-乙炔基苯基）乙基]甘氨酸和N-（4-乙炔基苄基）甘氨酸发生普拉托反应，合成了两种新的C_（60）键合的手性苯乙炔（3）和非手性苯乙炔（2）.含长烷基链的非手性苯乙炔2在氯仿中均聚，并与含3的光学活性苯乙炔在铑催化下共聚，得到可溶于氯仿的含C_（60）螺旋聚苯乙炔，而类似的无烷基链的非手性C_（60）苯乙炔（1）和3）的均聚物在普通有机溶剂中完全不溶。所得共聚物在主链区域和富勒烯发色区域均表现出诱导圆二色性（ICD），表明光学活性共聚物具有优先手性螺旋构象，且富勒烯侧基以螺旋阵列排列。
Two novel C60-bound chiral (3) and achiral (2) phenylacetylenes were synthesized by the treatment of C60 with (R)-N-[1-(4-ethynylphenyl)ethyl]glycine and N-(4-ethynylbenzyl)glycine by the Prato reaction in the presence of paraformaldehyde and dipentadecyl ketone, respectively. The homopolymerization of the achiral 2 bearing long alkyl chains and copolymerization with optically active phenylacetylenes including 3 using a rhodium catalyst in chloroform homogeneously occurred, giving the C60-containing helical poly(phenylacetylene)s soluble in chloroform, while the homopolymers of the analogous achiral C60-bound phenylacetylenes with no alkyl chain (1) and 3 were totally insoluble in common organic solvents. The obtained copolymers exhibited an induced circular dichroism (ICD) both in the main-chain region and in the fullerene chromophoric region, indicating that the optically active copolymers possess a preferred-handed helical conformation and that the pendant fullerene groups are arranged in helical array...