Department of Materials, ETH Zürich, Vladimir-Prelog-Weg 5, 8093, Zürich, Switzerland.
Small Molecule Crystallography Center (SMoCC), Department of Chemistry and Applied Biosciences, ETH Zürich, Vladimir-Prelog-Weg 1, 8093, Zürich, Switzerland.
Chemistry. 2018 Oct 9;24(56):15003-15012. doi: 10.1002/chem.201802513. Epub 2018 Sep 10.
In this work we present one of the rare cases of single-crystal-to-single-crystal (SCSC) linear polymerizations, resulting in a novel ladder-type polymer. The polymerization is based on the photoinduced [4+4]-cycloaddition reactions between trifunctional anthracene-based monomers. The careful design of the monomer anthraphane-tri(OMe), results in perfectly stacked anthracene pairs in the crystal structure, with Schmidt's distances d=3.505-3.666 Å and shift s=1.109 Å, allowing a selective linear polymerization in quantitative yields and in a matter of minutes, without compromising the integrity of the single crystals. The obtained polyanthraphane-tri(OMe), reveals moreover a very interesting and unprecedented case of stereoisomerism, which is characteristic for polyanthraphanes.
在这项工作中，我们展示了罕见的单晶到单晶（SCSC）线性聚合反应之一，得到了一种新型的梯形聚合物。聚合反应是基于三官能基蒽基单体的光诱导[4+4]-环加成反应。单体蒽三（甲氧基）的精心设计导致在晶体结构中形成完美堆积的蒽对，Schmidt 距离 d=3.505-3.666 Å 和位移 s=1.109 Å，允许在几分钟内以定量产率进行选择性线性聚合，而不会破坏单晶的完整性。所得到的聚蒽三（甲氧基）还揭示了一个非常有趣和前所未有的立体异构现象，这是聚蒽的特征。
