Fe–Pt Twisted Heterometallic Bicyclic Supramolecules via Multicomponent Self-Assembly

Herein, we describe a novel multicomponent self-assembly approach that has the prospect of furnishing unprecedented heterometallic bicyclic architectures with a high level of constitutional control. The methodology relies on the coordination directionality, and the stoichiometry of the individual precursor units, as well as on the difference of the coordination preference of the associated metal ions. As a proof-of-concept example, two aesthetically pleasing Fe-Pt heterometallic bicyclic metallacycles 6a and 6b, consisting of nine communicative components from four unique species, were prepared in ca. 70% isolated yields and fully characterized by multinuclear NMR, 2D NMR, electrospray ionization time-of-flight mass, and UV-vis spectroscopies. Furthermore, density functional theory based computations suggest that each of these supramolecular constructs encompasses two twisted [organo-Pt(II)←pyridine] coordination based irregular hexagons that are joined via a robust [terpyridine→Fe(II)←terpyridine] hinge.