受生物大分子螺旋结构的启发，人工螺旋聚合物引起了人们持续而广泛的研究兴趣。前期工作中，我们发现聚联烯能够形成稳定的螺旋构象。本申请项目我们将发展新的聚合方法，系统地研究利用非手性联烯单体合成手性的螺旋聚联烯。拟设计合成新型的手性镍配合物并用于非手性联烯的活性可控聚合，通过手性引发剂控制聚合反应的螺旋选择性，诱导生成光学活性的螺旋聚联烯；另一方面，我们拟在非手性联烯聚合过程中引入手性溶剂或诱导剂，诱导生成某一螺旋方向过量的光学活性螺旋聚联烯。探索聚合过程中的手性传递、诱导和放大的基本原理和规律。通过在光学活性的聚联烯侧基上引入羧基、氨基、硼酸等活性基团，利用主链的螺旋手性控制这类聚合物对手性胺、手性酸以及手性二醇的立体选择性络合，实现对这类化合物的手性识别和对映体分离，研究手性聚合物材料的回收和循环利用，发展新型高效的有机高分子手性识别和对映体分离材料。

Inspired by the helical structures of biomacromolecules, artificial helical polymers have attracted considerable and continuous research attentions in the past few decades. Recently, we found that well-defined polyallene can form stable helical conformation even in solution. Thus, in this proposal, we try to develope novel synthetic methods for facile synthesis of chiral helical polyallenes by using achiral allenic derivatives as monomers. We will design and synthesis of novel chiral nickel(II) complexes for promote the living/controlled polymerization of achiral allene monomers. The chiral Ni(II)-initiator may control the helix-sense selectivity of the polymerization, and induce one-handed predominated helical polyallenes. In addition, we will also explore the synthesis of chiral helical polyallenes from achiral allene monomers by using chiral solvent and other chiral compounds for the chiral inductions. The chiral transfer, induction, and amplification properties during the helix-sense selective polymerizations will also be investigated. Through which, we try to disclose the basic rules of the chiral transfer and amplification of the asymmetric polymerizations. By introduction of functional groups on the chiral helical polyallenes, these materials may be applied in the chiral recognition and enantiomeric separation. For example, incorporation of carboxyl acid, amine, and boric acids on the chiral polyallenes as the pendants, such materials may enantiomeric selectively complex with chiral amine, acid, and chiral diols, respectively, which result in the efficient chiral separation. Based on this researches, we hope to develope not only novel synthetic methods for chiral helical polymers but also optically active materials for chiral recognitions and enantiomeric separations.