Coordination-Driven Self-Assembly of Cyclometalated Iridium Squares Using Linear Aromatic Diisocyanides

Here, we demonstrate facile [4 + 4] coordination-driven self-assembly of cyclometalated iridium(III) using linear aryldiisocyanide bridging ligands (BLs). A family of nine new [Ir(C^N)₂(μ-BL)]₄⁴⁺ coordination cages is described, where C^N is the cyclometalating ligand-2-phenylpyridine (ppy), 2-phenylbenzothiazole (bt), or 1-phenylisoquinoline (piq)-and BL is the diisocyanide BL, with varying spacer lengths between the isocyanide binding sites. These supramolecular coordination compounds are prepared via a one-pot synthesis, with isolated yields of 40-83%. ¹H NMR spectroscopy confirms the selective isolation of a single product, which is affirmed to be the M₄L₄ square by high-resolution mass spectrometry. Detailed photophysical studies were carried out to reveal the nature of the luminescent triplet states in these complexes. In most cases, phosphorescence arises from the [Ir(C^N)₂]⁺ nodes, with the emission color determined by the cyclometalating ligand. However, in two cases, the lowest-energy triplet state resides on the aromatic core of the BL, and weak phosphorescence from that state is observed. This work shows that aromatic diisocyanide ligands enable coordination-driven assembly of inert iridium(III) nodes under mild conditions, producing supramolecular coordination complexes with desirable photophysical properties.