Molecular Tectonics: Design of Enantiopure Luminescent Heterometallic Ir(III)–Cd(II) Coordination Network

With the aim of combining luminescence and chirality in heterometallic Ir­(III)–Cd­(II) coordination networks, synthetic strategies for the formation of new Ir­(III)-based chiral metallatectons ([Ir­(dFppy)2(1)]­[PF6]), both as a racemic mixture of Δ and Λ enantiomers (rac-[Ir­(dFppy)2(1)]­[PF6]) and as enantiopure complexes (Δ-[Ir­(dFppy)2(1)]­[PF6] and Λ-[Ir­(dFppy)2(1)]­[PF6]), were developed. The final compounds were characterized both in solution and in the crystalline phase. Notably, their crystal structures were determined by single crystal X-ray diffraction, and their photophysical properties in solution and in the solid state were investigated. Combination of the cationic linear metallatecton with Cd2+ iodide salt ([CdI3]−), behaving as an anionic two-connecting node, leads to the formation of 1D chiral and neutral heterometallic Ir­(III)–Cd­(II) luminescent coordination networks both as a racemic mixture and as enantiomerically pure infinite architectures. The latter have been structurally studied in the solid state by X-ray diffraction both on single crystals and on microcrystalline powders. The infinite coordination networks display phosphorescence in the solid state at ca. 600 nm upon excitation at 400 nm.