Luminescent 1D heterometallic (Ir,Cd) coordination polymers based on bis-cyclometalated Ir() metallatectons and trinuclear Cd() dianionic nodes

Seven isostructural heterometallic luminescent (Ir,Cd) coordination polymers were prepared upon the combination of tris-chelate cationic Ir( iii ) complexes behaving as metalloligands with Cd( ii ) salts. Three octahedral Ir( iii ) complexes have been considered in the present report. They consist of a bipyridine unit functionalised with 3-pyridyl moieties as peripheral coordinating sites and two 2-phenylpyridyl cyclometalating derivatives. Three cadmium halide salts CdX 2 (X = Cl, Br, I) were used and rearranged themselves during the self-assembly process with the metallatectons to afford a dianonic trinuclear Cd node [Cd 3 X 8 ] 2− . Seven out of the nine possible metallotecton-metal salt combinations could be characterised in the crystalline phase by X-ray diffraction on single crystals proving the isostructurality of the seven extended architectures studied. All of the CPs are luminescent with small shifts observed in the emission wavelength compared to the discrete complexes. Depending on the degree of fluorination of the two cyclometalating units, tuning of the emission wavelength of the discrete complexes as well as of the resulting coordination polymers is achieved. Combination of three different 3-pyridyl substituted octahedral bis-cyclometalated Ir( iii ) metalloligands with Cd( ii ) salts afforded formation of emissive isostructural 1D heterometallic coordination polymers with a peculiar [Cd 3 X 8 ] 2− dianionic node.