Organoboron species can readily exist in two discrete hybridized forms that exhibit stark differences in excited state reactivity (Figure 1C, top). In its trigonal planar form boron has been shown to enable efficient EnT, due to conjugation of the boron p-orbital, while occupation via a dative interaction forming the tetrahedral boronate has rendered boron less efficient to sensitization. 15a In addition, hybridization has been shown to influence the intrinsic reactivity of α-boryl radicals, and consequently, we envisaged this would be an ideal model system to probe reaction pathways of non-symmetrical dienes. Specifically, we looked to explore if the boron motif, or hybridization state, has the potential to influence spin density upon excitation to promote alternative pathways (Figure , bottom), and assess what impact hybridization can have on intrinsic reactivity of the generated biradical.