Size Control of On-Surface Self-Assembled Nanochains Using Soft Building Blocks.
Size Control of On-Surface Self-Assembled Nanochains Using Soft Building Blocks.
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DOI：
10.1021/acs.jpclett.3c02858
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发表时间：
2023-12
期刊：
影响因子：
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通讯作者：
Yang Song;Zhanbo Li;Rongyu Tang;Kun Zhou;Lizhi Zhang;Tao Lin;Jian Fan;Ziliang Shi;Y. Ma
中科院分区：
文献类型：
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作者：
Yang Song;Zhanbo Li;Rongyu Tang;Kun Zhou;Lizhi Zhang;Tao Lin;Jian Fan;Ziliang Shi;Y. Ma
由于其构象灵活性，具有侧链的软分子在分子自组装或自组织过程中自下而上构建超分子纳米结构中发挥着至关重要的作用。然而，旋转侧链在有限空间中的影响以及随后的表面限制超分子自组装仍然很少被探索。在此，利用软构件之间的空间限制效应，通过排斥性空间位阻和吸引性化学相互作用之间的协同作用，实现了表面限制超分子配位自组装的尺寸控制。将扫描隧道显微镜与密度泛函理论计算和蒙特卡罗模拟相结合，我们阐明了软构件的热摆动运动产生的有效排斥力，从而可以调整自组装链结构的长度。通过空间限制效应引起的排斥相互作用和配位化学相互作用之间的微妙平衡，我们提供了一种控制表面超分子纳米结构几何形状的新策略。
Owing to their conformational flexibility, soft molecules with side chains play a crucial role in molecular self-assembly or self-organization processes toward bottom-up building of supramolecular nanostructures. However, the influence of the rotating side chains in the confined space and subsequent surface-confined supramolecular self-assembly remains rarely explored. Herein, using the spatial confinement effect between soft building blocks, we realized size control on surface-confined supramolecular coordination self-assembly through the synergy between the repulsive steric hindrance and the attractive chemical interactions. Combining scanning tunneling microscopy with density functional theory calculations and Monte Carlo simulations, we elucidated the effective repulsive force generated by the thermal wiggling motions of the soft building blocks, allowing length tuning of the self-assembled chain structures. Through a delicate balance between the repulsive interaction induced by the spatial confinement effect and the coordinate chemical interaction, we provide a new strategy for controlling the geometry of the on-surface supramolecular nanostructures.