Design, Synthesis, and Characterization of Novel Phosphorus-Containing Conjugated Materials Based on Vat Orange 3

Abstract

As the global production and diversification of electronic devices—ranging from energyconversion to energy-storage applications—continues to surge, enhancing their efficiency has become a critical objective. While the well-built metal-based technology of these devices warrants recognition, the associated sustainability and toxicity issues must not be overlooked. This is where π-conjugated organic materials play a pivotal role. Research in the new millennium has provided numerous types of conjugated materials possessing properties that offer clear paths towards integrated electronic devices (e.g., Organic Light-Emitting Devices (OLEDs), Organic Solar Cells (OSCs), Organic Field-Effect Transistors (OFETs), organic batteries) with performances approaching those of their metal-based counterparts. Accordingly, a multitude of developed compounds such as Polycyclic Aromatic Hydrocarbons (PAHs) or strategies that embed main group elements into carbon-based synthons, have all been aimed at this common goal. However, the development of PAHs and incorporation of heaver main group elements such as phosphorus have rarely intersected until recently. This marriage is facilitated by the emergence of vat dyes as cost-effective precursors for organic semiconductors as their scaffolds provide a convenient route to PAH cores, such as anthanthrene and chrysene. Therefore, this thesis is focused on methods of merging phosphacycles with Vat Orange 3, along with investigating the photophysics of these functional materials, their capacity and ease of undergoing redox processes, and the role of phosphorus in modulating the systems’ electronics and impact on the overall functional properties. Through bridging heavier main group elements and large conjugated scaffolds, the emerging platform also attempts to overcome long-standing limitations in the literature, such as inefficient low-energy luminescence, restoration of the original keto groups in the vat dye-based frameworks, and doublet emission from phosphorus-containing conjugated materials.