Steric Pressure in Heteropentacenes Modulates the Photophysical Properties – A Molecular Design Strategy for Functional Materials

Abstract

Discovering the versatile ability of environmental-independent solution- and solid-state emission (SSSE) enabled new possibilities of fine-tuning photophysical properties, targeting specific organelles, or developing remarkable materials. Herein, we report an unprecedented design concept for SSSE by employing the “magic methyl” effect in a series of alkylated heteropentacyclic luminophores R8, Y8,and G8. Implementing an increasing amount of ortho-methyl groups influences the vertical electronic transitions, tuning the emission colors from red over yellow to green and inverting the preferred state of luminescence from solution to solely the solid-state or even both. An in-depth analysis was performed using X-ray diffractometric structure elucidation, packing analysis and density functional theory calculations to correlate the photophysical properties with the steric pressure induced by the methyl groups. Additionally, the application scope of these new materials was investigated. Mesoporous silica nanoparticles loaded with the three new luminophores were prepared and employed as additives for 3D printing using stereolithography. Ultimately, these stimuli-responsive molecules performed as optical sensors of microenvironmental temperature and phase transition changes in liquid crystals.