Emissive supramolecular ionic crystals combining a red-NIR phosphorescent [Re 6 Se 8 CN 6 ] 4- cluster anion and a blue fluorescent tetraphenylethene counter-cation.

A blue fluorescent tetraphenylethylene-based dication and a red-NIR phosphorescent rhenium octahedral cluster tetra-anion are associated electrostatically to generate a supramolecular ionic framework which crystallizes in the P 1̄ centric space group. The emission properties of the hybrids are studied in the crystalline state and in solution revealing a resonant energy transfer and a high sensitivity toward oxygen.