New organic–inorganic hybrid materials based on perylene diimide–polyhedral oligomeric silsesquioxane dyes with reduced quenching of the emission in the solid state

Solid state luminescent materials are the subject of ever growing interest both from a scientific and a technological point of view because high-tech applications of light emitting materials very often require their use in the condensed phase. Aggregation caused quenching processes however represent an obstacle to the development of most luminogens in the condensed phase. This is why particularly fascinating are those materials showing high emission intensity in the solid state. Aggregation caused quenching is particularly detrimental for π-extended polycyclic aromatic hydrocarbons, for example perylene tetracarboxylic acid diimides which are characterized by a near-unity fluorescence quantum yield in solution but are far less emissive in the solid state.Here we report on the easy preparation and on the optical investigation of perylene tetracarboxylic acid diimide derivatives linked to the inorganic cage of polyhedral oligomeric silsesquioxanes. These new hybrid perylene diimide–polyhedral oligomeric silsesquioxane dyes show in solution the typical absorption and emission features of the perylene diimide fragment, with a quantum efficiency close to unity. Moreover, in the solid state (both as spin-coated films and powders) the electronic absorption spectra indicate a reduced fluorophore aggregation and significant quantum yield efficiencies induced by the positive effect of the polyhedral oligomeric silsesquioxane cage.

Graphical AbstractFigure optionsDownload as PowerPoint slideHighlights
► New soluble perylenes linked to polyhedral oligomeric silsesquioxanes cages.
► Hybrid perylene–silsesquioxane dyes show reduced aggregation caused quenching.
► Hybrid perylene–silsesquioxane dyes show enhanced red emission in the solid state.
► Bulky silsesquioxanes reduce aggregation caused quenching phenomena in perylene dyes.