To avoid the issues associated with handling low-molecular-weight strained hydrocarbons, electrondeficient BCB 1a, known to be non-volatile and easily synthesised, was investigated (Fig. ). Although this species contains an electron-withdrawing group directly appended to the σ-framework, cyclic voltammetry studies clearly showed that this compound could be oxidised, with a half-wave potential of +1.79 V vs Ag/AgCl (2 M LiCl in EtOH). Density functional theory (DFT) calculations of the condensed Hirshfeld charges and spin densities of the radical cation revealed that both the overall charge and the spin were largely delocalised across the bridging bond of the BCB framework as well as the aromatic ring (Fig. ). Analysing these values revealed that the C1 and C3 carbon atoms have a greater contribution of the overall spin (0.31 and 0.15, respectively) compared to the positive charge (0.10 and 0.10, respectively), which is more concentrated on the aryl ring (0.41). Additionally, the bridging bond remains intact upon oxidation and shows an elongation of just 0.16 Å compared to the ground state , highlighting the difference between this activation strategy and energy transfer, where σ-bond cleavage to form the corresponding diradical occurs .