Employing 4-ethynylaniline as a simple organic ligand we were able to prepare the stable trans-bis(acetylide)platinum(II) complex [Pt(L¹)₂(PBu₃)₂] as a linear metalloligand. The reaction of this metalloligand with iron(II) cations and pyridine-2-carbaldehyde according to the subcomponent self-assembly approach yielded decanuclear heterobimetallic tetrahedron [Fe₄Pt₆(L²)₁₂](OTf)₈. Thus, combination of these two design concepts – the subcomponent self-assembly strategy and the complex-as-a-ligand approach – ensured a fast and easy synthesis of large heterobimetallic coordination cages of tetrahedral shape with a diameter of more than 3 nm as a mixture of all three possible T-, S₄- and C₃-symmetric diastereomers. The new complexes were characterized by NMR and UV–vis spectroscopy and ESI mass spectrometry. Using GFN2-xTB we generated energy-minimized models of the diastereomers of this cage that further corroborated the results from analytical findings.

中文翻译：

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来自线性铂(II)-双(乙炔)金属配体的异双金属四面体

使用4-乙炔基苯胺作为简单的有机配体，我们能够制备稳定的反式-双(乙炔)铂(II)络合物[Pt(L ¹ ) ₂ (PBu ₃ ) ₂ ]作为线性金属配体。该金属配体与铁(II)阳离子和吡啶-2-甲醛根据子组分自组装方法反应生成十核异双金属四面体[Fe ₄ Pt ₆ (L ² ) ₁₂ ](OTf) ₈。因此，这两种设计理念的结合——子组件自组装策略和复合物作为配体方法——确保了快速、轻松地合成直径超过 3 nm 的四面体形状的大型异双金属配位笼作为所有三种可能的T-、S ₄ -和C _{3 -}对称非对映异构体的混合物。通过核磁共振、紫外可见光谱和 ESI 质谱对新配合物进行了表征。使用 GFN2-xTB，我们生成了该笼的非对映异构体的能量最小化模型，进一步证实了分析结果。