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探索手性纤维素纳米晶体薄膜的圆二色性,以获得超分子聚合物的光控手性螺旋。

Exploring the Circular Polarization Capacity from Chiral Cellulose Nanocrystal Films for a Photo-Controlled Chiral Helix of Supramolecular Polymers.

机构信息

Key Laboratory of Bio-based Material Science and Technology of Ministry of Education, Northeast Forestry University, 26 Hexing Road, Harbin, 150040, P. R. China.

Department of Chemistry and Chemical Engineering, College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, 26 Hexing Road, Harbin, 150040, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2022 Apr 25;61(18):e202117042. doi: 10.1002/anie.202117042. Epub 2022 Feb 28.

Abstract

Circularly polarized light (CPL) is key to asymmetric photochemistry as it could impart the chiral organization information into chemical products. Here, we demonstrate the circular polarization capacity of chiral cellulose nanocrystal (CNC) films to trigger photo-alignment of achiral supramolecular polymers into helical structures. Right-handed transmitted (T-) CPL was generated from self-assembled CNC films, which induced amorphous azobenzene (Azo) supramolecular polymers into chiral structures. The chiral induction effect of T-CPL is enhanced on Azo polymers with longer spacers. The absorptive dissymmetry factor (g ) values of liquid-crystal supramolecular polymers can be amplified significantly (over 10 times) after T-CPL irradiation. Moreover, by integrating carbon dots into CNC films, CPL emission with a considerable luminescence dissymmetry factor (g ) up to -0.66 was achieved, and it could be used for the photo-alignment of Azo polymers with high chiroptical properties. This work provides new insight for the photo modulation of supramolecular polymers by CPL-active materials.

摘要

圆偏振光(CPL)是不对称光化学反应的关键,因为它可以将手性组织信息赋予化学产物。在这里,我们证明了手性纤维素纳米晶体(CNC)薄膜的圆偏振能力可以将非手性超分子聚合物触发光取向为螺旋结构。自组装的 CNC 薄膜产生了右旋透射(T-)CPL,它诱导无定形偶氮苯(Azo)超分子聚合物形成手性结构。具有更长间隔基的 Azo 聚合物的 T-CPL 的手性诱导效应增强。液晶超分子聚合物的吸收不对称因子(g)值在 T-CPL 照射后可以显著放大(超过 10 倍)。此外,通过将碳点集成到 CNC 薄膜中,实现了具有相当大的发光不对称因子(g)高达-0.66 的 CPL 发射,并且可以用于具有高手性性质的 Azo 聚合物的光取向。这项工作为 CPL 活性材料对超分子聚合物的光调制提供了新的见解。

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