Joint Venture of Metal Cluster and Amphiphilic Cationic Minidendron Resulting in Near Infrared Emissive Lamellar Ionic Liquid Crystals

Inorganic red‐NIR emissive materials are particularly relevant in many fields like optoelectronic, bioimaging or solar cells. Benefiting from their emission in devices implies their integration in easy‐to‐handle materials like liquid crystals, whose long‐range ordering and self‐healing abilities could be exploited and influence emission. Herein, we present red‐NIR emissive hybrid materials obtained with phosphorescent octahedral molybdenum cluster anions electrostatically associated with amphiphilic guanidinium minidendrons. Polarized optical microscopy and X‐ray analysis show that while the minidendron chloride salts self‐organize into columnar phases, their association with the dianionic metal cluster leads to layered phases. Steady‐state and time‐resolved emission investigations demonstrate the influence of the minidendron alkyl chain length on the phosphorescence of the metal cluster core. Guanidinium minidendrons bearing terminal aliphatic chains show a columnar liquid‐crystalline behaviour once associated with chlorine anions, whereas they turned into layered phases when associated with phosphorescent octahedral molybdenum cluster dianions. The emission properties of the inorganic dyes are largely influenced by the minidendron chain length in these first‐of‐their‐kind clustomesogens.