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基于铂配合物的圆偏振发光活性超分子纳米管,其经历动态形态转变和螺旋性反转。

Circularly Polarized Luminescence Active Supramolecular Nanotubes Based on Pt Complexes That Undergo Dynamic Morphological Transformation and Helicity Inversion.

作者信息

Kang Seok Gyu, Kim Ka Young, Cho Yumi, Jeong Dong Yeun, Lee Ji Ha, Nishimura Tomoki, Lee Shim Sung, Kwak Sang Kyu, You Youngmin, Jung Jong Hwa

机构信息

Department of Chemistry and Research Institution of Natural Sciences, Gyeongsang National University (GNU), Jinju, 52828, Republic of Korea.

Department of Energy Enginerring, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, 44919, Republic of Korea.

出版信息

Angew Chem Int Ed Engl. 2022 Sep 19;61(38):e202207310. doi: 10.1002/anie.202207310. Epub 2022 Jul 8.

Abstract

Circularly polarized luminescence (CPL) with tunable chirality is currently a challenging issue in the development of supramolecular nanomaterials. We herein report the formation of helical nanoribbons which grow into helical tubes through dynamic helicity inversion. For this, chiral Pt complexes of terpyridine derivatives, namely S-trans-1 and R-trans-1, with respective S- and R-alanine subunits and incorporating trans-double bonds in the alkyl chain were prepared. In DMSO/H O (5 : 1 v/v), S-trans-1 initially forms a fibrous self-assembled product, which then undergoes dynamic transformation into helical tubes (left-handed or M-type) through helical ribbons (right-handed or P-type). Interestingly, both helical supramolecular architectures are capable of emitting CPL signals. The metastable helical ribbons show CPL signals (g =±4.7×10 ) at 570 nm. Meanwhile, the nanotubes, which are the thermodynamic products, show intense CPL signals (g =±5.6×10 ) at 610 nm accompanied by helicity inversion. This study provides an efficient way to develop highly dissymmetric CPL nanomaterials by regulating the morphology of metallosupramolecular architectures.

摘要

在手性可调的圆偏振发光(CPL)是目前超分子纳米材料发展中的一个具有挑战性的问题。我们在此报告了螺旋纳米带的形成,其通过动态螺旋反转生长为螺旋管。为此,制备了具有各自S-和R-丙氨酸亚基且在烷基链中含有反式双键的三联吡啶衍生物的手性铂配合物,即S-反式-1和R-反式-1。在DMSO/H₂O(5∶1 v/v)中,S-反式-1最初形成纤维状自组装产物,然后通过螺旋带(右手或P型)动态转变为螺旋管(左手或M型)。有趣的是,两种螺旋超分子结构都能够发射CPL信号。亚稳螺旋带在570 nm处显示CPL信号(g =±4.7×10⁻³)。同时,作为热力学产物的纳米管在6¹⁰nm处显示强烈的CPL信号(g =±5.6×10⁻³),并伴有螺旋反转。这项研究提供了一种通过调节金属超分子结构的形态来开发高度不对称CPL纳米材料的有效方法。

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