Research Center in Biological Chemistry and Molecular Materials (CiQUS), Universidade de Santiago de Compostela, E-15782, Santiago de Compostela, Spain.
University of Münster, Institute of Organic Chemistry, Corrensstraße 36, 48149, Münster, Germany.
Nat Commun. 2023 Jun 8;14(1):3348. doi: 10.1038/s41467-023-39014-2.
Supramolecular and covalent polymers share multiple structural effects such as communication mechanisms among monomer repeating units, which are related to their axial helical structure. Herein, a unique multi-helical material combining information from both metallosupramolecular and covalent helical polymers is presented. In this system, the helical structure described by the poly(acetylene) (PA) backbone (cis-cisoidal, cis-transoidal) guides the pendant groups in a fashion where a tilting degree emerges between a pendant and the adjacent ones. As a result, a multi-chiral material is formed comprising four or five axial motifs when the polyene skeleton adopts either a cis-transoidal or cis-cisoidal configuration: the two coaxial helices-internal and external-and the two or three chiral axial motifs described by the bispyridyldichlorido Pt complex array. These results show that complex multi-chiral materials can be obtained by polymerizing appropriate monomers that combine both point chirality and the ability to generate chiral supramolecular assemblies.
超分子聚合物和共价聚合物具有多种结构效应,例如单体重复单元之间的通讯机制,这与它们的轴向螺旋结构有关。本文提出了一种独特的多螺旋材料,它结合了金属超分子和共价螺旋聚合物的信息。在该体系中,聚乙炔(PA)主链(顺式-顺式,顺式-反式)描述的螺旋结构以一种方式引导侧基,在侧基和相邻侧基之间出现倾斜程度。结果,当聚烯骨架采用顺式-反式或顺式-顺式构型时,形成了包含四个或五个轴向基序的多手性材料:两个同轴螺旋——内螺旋和外螺旋——以及由双吡啶二氯代铂配合物阵列描述的两个或三个手性轴向基序。这些结果表明,通过聚合适当的单体,可以获得复杂的多手性材料,这些单体结合了点手性和生成手性超分子组装的能力。