Drastic solid-state luminescence color tuning of an archetypal Ir(iii) complex using polyoxometalates and its application as a vapoluminescence chemosensorElectronic supplementary information (ESI) available: Detailed syntheses of Ir2Mo8-A, Ir2Mo8-B, Ir4Mo8, Ir2Mo4, and Ir2W6, FT-IR spectra and powder XRD patterns of Ir2Mo8-A and Ir2Mo8-B, 1H NMR and TGA measurements of Ir2Mo8-A, complementary optical characterizations, and X-Ray crystallographic data. CCDC 1505014-1505017. For ESI and crystallo

Using a straightforward one-step synthetic procedure, the solid-state phosphorescence of the archetypal [Ir III (ppy) 2 (bpy)] + complex has been successfully tuned from green to yellow, orange and red by its association with a series of polyoxometalates. Such new materials can exhibit remarkable vapoluminescence properties for the detection of volatile organic compounds (VOCs) even in the presence of moisture via a new polymorphous conversion mechanism. New assemblies based on the archetypal [Ir III (ppy) 2 (bpy)] + complex and a series of polyoxometalates exhibit highly tunable phosphorescence and vapoluminescence properties for detection of volatile organic compounds.