We investigated the self‐assembly process of a Pd₄L₈ double‐walled square (DWS) from [PdPy*₄]²⁺ (Py*: 3‐chloropyridine used as the leaving ligand on the Pd^II center) and an organic ditopic ligand by QASAP (quantitative analysis of self‐assembly process). DWS is assembled mainly through three pathways. Within 5 minutes of the self‐assembly, all of the substrates, the metal source and the organic ditopic ligand, were completely consumed and converted into primary intermediates. In 2 h, the primary intermediates afforded 30 % of DWS, 200‐nm‐sized large intermediates, and a relatively stable transient intermediate. This stable intermediate was characterized as a kinetically trapped Pd₃L₆ double‐walled triangle (DWT) by NMR and mass measurements. From 2 h to 1 day, 19 % of DWS was formed from the 200‐nm‐sized large intermediate with the aid of Py*, which is not a component of the final assembly. After 1 day, the remaining large intermediate and DWT afforded 39 % of DWS with the aid of Py* again. This self‐assembly process is quite different from that of previously reported single‐walled macrocycles, and the change in the self‐assembly pathway would arise from the difference in the flexibility of ditopic ligands. This study revealed a complicated multiplicity, not a simple single pathway, of the self‐assembly process of DWS.

中文翻译：

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Pd4L8双壁正方形的自组装部分是通过运动诱捕物种的形成而发生的

我们研究了由[PdPy * ₄ ] ²⁺（Py *：3-氯吡啶用作Pd ^II中心的离去配体）的Pd ₄ L ₈双壁方形（DWS）的自组装过程通过QASAP进行配体（自组装过程的定量分析）。DWS主要通过三个途径进行组装。自组装后5分钟内，所有底物，金属来源和有机二位配体被完全消耗，并转化为主要中间体。在2小时内，主要中间体提供了30％的DWS，200纳米大小的大型中间体和相对稳定的瞬态中间体。通过NMR和质量测量将该稳定的中间体表征为动力学捕获的Pd ₃ L ₆双层三角形（DWT）。从2小时到1天，借助于Py *，由200 nm大小的大中间体形成了19％的DWS，而Py *并不是最终组装的组成部分。1天后，其余的大型中间体和DWT提供了39％的DWS再次借助Py *。这种自组装过程与以前报道的单壁大环化合物完全不同，并且自组装途径的变化将来自对位配体灵活性的差异。这项研究揭示了DWS自组装过程的复杂性，而不是简单的单一途径。