Inorganic Chemistry, Vol.58, No.14, 8900-8905, 2019
Photoactive Hexanuclear Molybdenum Nanoclusters Embedded in Molecular Organogels
Hexanuclear molybdenum clusters are attractive species because of their outstanding photonic properties, and in the past they have been attached to a variety of supports such as organic polymers and inorganic nanoparticles, as described in the recent literature. Here, a cluster of the formula TBA(2)[Mo6I8Ac6] (TBA = tetrabutylammonium; Ac = acetate) has been supported on molecular organogels for the first time, resulting in a new soft material with remarkable photoactivity. Electron and confocal microscopic analyses showed the alignment of the nanoclusters to 1D self-assembled fibers formed by the organic gelator, and emission spectroscopy corroborated the interaction of the emissive clusters with such fibrillary structures. The new hybrid system is a deep-red emissive material (phosphorescence maximum at ca. 680 nm), with chromatic coordinates x = 0.725 and y = 0.274, capable of efficiently generating singlet oxygen (O-1(2)) upon illumination with white light, as demonstrated by the photooxygenation of 9,10-dimethylanthracene and 1,5-dihydroxynaphthalene. The organogels can been made in dichloromethane and toluene and in both solvents display phosphorescence emission and photocatalytic properties.