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

Employing 4-ethynylaniline as a simple organic ligand we were able to prepare the stable trans-bis(acetylide)platinum(II) complex [Pt(L(1))(2)(PBu(3))(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 [Fe(4)Pt(6)(L(2))(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-, S(4)- and C(3)-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.