A heterobimetallic tetrahedron from a linear platinum(II)-bis(acetylide) metalloligand

• Main Authors: Matthias Hardy, Marianne Engeser, Arne Lützen
• Format: Article
• Language: English
• Published: Beilstein-Institut 2020-11-01
• Series: Beilstein Journal of Organic Chemistry
• Subjects: cage compounds; heterobimetallic complexes; pyridylimine ligands; self-assembly; supramolecular chemistry
• Online Access: https://doi.org/10.3762/bjoc.16.220

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.