Beads on a Chain Fluorescent Oligomeric Materials: Interactions of Conjugated Organic Cross-Linkers with Silsesquioxane Cages

Organic electronic materials have advantages over inorganics in terms of versatility, cost, and processability. Recent advancements in organic materials for light-emitting diodes (OLED), field effect transistors (OFET), and photovoltaics have engendered extensive innovation potential on this field. In this research, we focus on synthesizing SQ (silsesquioxane) based oligomers cross-linked by dibromo-aromatic linkers and explore how the cross-linker influences their photophysical properties. Bis-trialkoxy silyl (linker) model compounds were synthesized to compare noncage photophysical properties with the oligomers. Several techniques such as UV/vis, fluorescence, FTIR, and thermal gravimetric analysis (TGA) have been used to characterize the systems. Time-resolved fluorescence and femtosecond transient absorption spectroscopy were used to understand the excited state dynamics of these materials. Studies were carried out to understand the differences between monomers and oligomers and potential energy transfer and charge transfer between the cages and cross-linking chromophores. Transient absorption showed lower energy absorption from the excited states, suggesting short-range communication between moieties. Single photon counting studies have shown distinct lifetime differences between most linkers and cages display possible excitation energy transfer through these materials. Transient absorption anisotropy measurements have shown signatures for excitation energy transfer between linker chromophores for oligomeric compounds. The silsesquioxane (SQ) backbone of the oligomers gives substantial thermal stability as well as solution processability, giving better flexibility for achieving energy transfer between linking chromophores.

Automated summary

Advancements in organic materials for devices like OLEDs, OFETs, and photovoltaics have shown great innovation potential. This research focuses on synthesizing SQ-based oligomers cross-linked by dibromo-aromatic linkers to explore their photophysical properties, using techniques such as UV/vis, fluorescence, FTIR, and TGA for characterization and understanding excited state dynamics. The study also investigates potential energy transfer and charge transfer within the materials, revealing short-range communication between moieties and significant thermal stability and solution processability of the SQ backbone in achieving energy transfer.