基于具有C2对称手性[60]富勒烯双加合物的聚（苯乙炔）的大分子螺旋诱导

Macromolecular helicity induction on a poly(phenylacetylene) with C2-symmetric chiral [60]fullerene-bisadducts.

作者信息

Nishimura Tatsuya, Tsuchiya Kayo, Ohsawa Sousuke, Maeda Katsuhiro, Yashima Eiji, Nakamura Yosuke, Nishimura Jun

机构信息

Contribution from the Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Chikusa-ku, Nagoya 464-8603, Japan.

出版信息

J Am Chem Soc. 2004 Sep 22;126(37):11711-7. doi: 10.1021/ja046633l.

DOI:10.1021/ja046633l

PMID:15366919

Abstract

Three chiral N-methylfulleropyrrolidine bisadducts were prepared, isolated, and completely resolved into each enantiomer using a chiral HPLC column, which were then converted to the corresponding optically active, cationic C(60)-bisadducts to investigate if they could act as a macromolecular helicity inducer in a poly(phenylacetylene) bearing an anionic monoethyl phosphonate pendant (poly-1) in aqueous solution. Upon complexation with the chiral C(60)-bisadducts, only the trans-3 bisadduct exhibited the characteristic induced circular dichroism (ICD) in the UV-visible region of the polymer backbone in dimethyl sulfoxide-water mixtures due to the predominantly one-handed helix formation of poly-1, while the trans-2 and cis-3 bisadducts induced almost no apparent CD in the same region. These results indicate that the helicity induction on poly-1 is highly sensitive to the structure and geometry of the cationic C(60)-bisadducts with a different distance between the separated charges.

摘要

制备了三种手性N-甲基富勒吡咯烷双加合物，通过手性高效液相色谱柱将其分离并完全拆分为每种对映体，然后将它们转化为相应的具有光学活性的阳离子C(60) -双加合物，以研究它们在水溶液中能否作为带有阴离子单乙基膦酸酯侧基的聚（苯乙炔）（聚-1）中的大分子螺旋诱导剂。与手性C(60) -双加合物络合后，由于聚-1主要形成单手螺旋，只有反式-3双加合物在二甲基亚砜-水混合物中聚合物主链的紫外-可见区域表现出特征性的诱导圆二色性（ICD），而反式-2和顺式-3双加合物在同一区域几乎没有诱导出明显的圆二色性。这些结果表明，聚-1上的螺旋诱导对具有不同电荷间距的阳离子C(60) -双加合物的结构和几何形状高度敏感。