A BODIPY‐based bis(3‐pyridyl) ligand undergoes self‐assembly upon coordination to tetravalent palladium(II) cations to form a Pd₆L₁₂ metallosupramolecular assembly with an unprecedented structural motif that resembles a rotaxane‐like cage‐in‐ring arrangement. In this assembly the ligand adopts two different conformations—a C‐shaped one to form a Pd₂L₄ cage which is located in the center of a Pd₄L₈ ring consisting of ligands in a W‐shaped conformation. This assembly is not mechanically interlocked in the sense of catenation but it is stabilized only by attractive π‐stacking between the peripheral BODIPY chromophores and the ligands’ skeleton as well as attractive van der Waals interactions between the long alkoxy chains. As a result, the co‐arrangement of the two components leads to a very efficient space filling. The overall structure can be described as a rotaxane‐like assembly with a metallosupramolecular cage forming the axle in a metallosupramolecular ring. This unique structural motif could be characterized via ESI mass spectrometry, NMR spectroscopy, and X‐ray crystallography.

中文翻译：

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金属碳素超分子Pd6L12聚集体的类似轮烷的笼中环结构基序。

一个基于BODIPY的双（3-吡啶基）配体在与四价钯（II）阳离子配位后经历自组装，形成具有前所未有的结构基序的Pd ₆ L ₁₂金属超分子组装体，类似于轮烷样的笼中环排列。在这种组装中，配体采用两种不同的构象-一个C形构象形成一个Pd ₂ L ₄笼，该笼位于Pd ₄ L ₈的中心由W型构象的配体组成的环。这种组装在机械意义上不是机械联锁的，而是仅通过外围BODIPY生色团与配体骨架之间的吸引π堆积以及长烷氧基链之间的吸引范德华相互作用来稳定。结果，两个组件的共同布置导致非常有效的空间填充。整体结构可以说是轮状烷状组件，带有金属超分子笼，形成金属超分子环中的轴。这种独特的结构基序可以通过ESI质谱，NMR光谱和X射线晶体学进行表征。