Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.
Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China.
J Am Chem Soc. 2021 Jan 13;143(1):442-452. doi: 10.1021/jacs.0c11752. Epub 2020 Dec 28.
The organization of molecular motors in supramolecular assemblies to allow the amplification and transmission of motion and collective action is an important step toward future responsive systems. Metal-coordination-driven directional self-assembly into supramolecular metallacycles provides a powerful strategy to position several motor units in larger structures with well-defined geometries. Herein, we present a pyridyl-modified molecular motor ligand () which upon coordination with geometrically distinct di-Pt(II) acceptors assembles into discrete metallacycles of different sizes and shapes. This coordination leads to a red-shift of the absorption bands of molecular motors, making these motorized metallacycles responsive to visible light. Photochemical and thermal isomerization experiments demonstrated that the light-driven rotation of the motors in the metallacycles is similar to that in free in solution. CD studies show that the helicity inversions associated with each isomerization step in the rotary cycle are preserved. To explore collective motion, the trimeric motor-containing metallacycle was aggregated with heparin through multiple electrostatic interactions, to construct a multi-component hierarchical system. SEM, TEM, and DLS measurements revealed that the photo- and thermal-responsive molecular motor units enabled selective manipulation of the secondary supramolecular aggregation process without dissociating the primary metallacycle structures. These visible-light-responsive metallacycles, with intrinsic multiple rotary motors, offer prospects for cooperative operations, dynamic hierarchical self-assembled systems, and adaptive materials.
将分子马达在超分子组装体中的组织以允许运动和集体行动的放大和传递是朝向未来响应系统的重要步骤。金属配位驱动的定向自组装成超分子金属环提供了一种强大的策略，可将几个马达单元定位在具有明确定义的几何形状的较大结构中。在此，我们提出了一种吡啶修饰的分子马达配体（），其与几何上不同的双-Pt(II)受体配位后组装成不同大小和形状的离散金属环。这种配位导致分子马达的吸收带红移，使这些机动金属环对可见光有响应。光化学和热异构化实验表明，金属环中马达的光驱动旋转类似于在溶液中自由的旋转。CD 研究表明，旋转循环中每个异构化步骤相关的螺旋反转得以保留。为了探索集体运动，通过多个静电相互作用将包含三联体马达的金属环与肝素聚集在一起，构建了一个多组分分级系统。SEM、TEM 和 DLS 测量表明，光热响应的分子马达单元能够选择性地操纵次级超分子聚集过程，而不会解离主要金属环结构。这些具有内在多个旋转马达的可见光响应金属环为合作操作、动态分级自组装系统和自适应材料提供了前景。
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