Okuda Shogo, Ikai Tomoyuki, Okutsu Hinako, Ando Mitsuka, Hattori Masaki, Ishidate Ryoma, Yashima Eiji
Department of Molecular and Macromolecular Chemistry Graduate School of Engineering, Nagoya University Chikusa-ku, Nagoya, 464-8603, Japan.
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST) Kawaguchi, Saitama, 332-0012, Japan.
Angew Chem Int Ed Engl. 2024 Nov 4;63(45):e202412752. doi: 10.1002/anie.202412752. Epub 2024 Sep 12.
We report the helix-sense-selective memory polymerization (HSMP) of achiral biphenylylacetylenes bearing carboxy and amino pendant groups in the presence of basic and acidic chiral guests in water, respectively. The HSMP proceeds in a highly helix-sense-selective manner driven by noncovalent chiral ionic interactions between the monomers and guests under kinetic control, producing the one-handed helical polymers with a static memory of helicity in one-pot during the polymerization in a very short time, accompanied by amplification of asymmetry. The carboxy-bound helicity-memorized polymer self-assembles into a cholesteric liquid crystal in concentrated water, in which a variety of basic achiral fluorophores further co-assembles to form supramolecular helical aggregates that exhibit an induced circularly polarized luminescence in a color tunable manner.
我们分别报道了在水相中，带有羧基和氨基侧基的非手性联苯乙炔在碱性和酸性手性客体存在下的螺旋方向选择性记忆聚合（HSMP）。在动力学控制下，HSMP通过单体与客体之间的非共价手性离子相互作用以高度螺旋方向选择性的方式进行，在极短时间内的聚合过程中一锅法生成具有螺旋静态记忆的单手螺旋聚合物，同时伴随着不对称性的放大。羧基连接的螺旋记忆聚合物在浓水中自组装成胆甾型液晶，其中各种碱性非手性荧光团进一步共组装形成超分子螺旋聚集体，以颜色可调的方式表现出诱导圆偏振发光。
