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P-heteroannulation on perylene diimides in one pot is presented. The resulting phosphaperylene diimides demonstrate unique molecular structures with an out-of-plane dipole moment of 8.10 D. Photophysical characterization reveals degenerated LUMO levels as low as -4.4 eV and remarkable absorption redshifts extending to 579 nm. High fluorescence quantum yields (ϕF) of up to 94% make them promising photoluminescent materials. Diffuse intrinsic pontine glioma (DIPG) remains a fatal brainstem tumor demanding innovative therapies. As B7-H3 (CD