When using E-stilbene as the substrate, pDTCz-DPmS successfully forms the isomeric product, although only does so in moderate yield of 63% while for 4CzIPN, the yield of the Z isomer is higher at 87%. This is a result of 4CzIPN possessing a more suitable ET to sensitize the E-isomer while the ET for pDTCz-DPmS is considerably higher, and thus there is a lack of chemoselectivity to selectively sensitize only the Eisomer. By contrast, when exploring the E/Z isomerization of diisopropyl fumarate (Figure ), a higher triplet energy alkene (ET = 2.7 eV and 3.1 eV, respectively, for the E and Z isomers), 38 pDTCz-DPmS provides a significantly greater yield than 4CzIPN (81% and 6%, respectively), as well as outperforming the literature photocatalyst Finally, we investigated the potential of pDTCz-DPmS in a commonly used Ni-cocatalyzed metallaphotocatalysis reaction involving the cross-coupling of carboxylic acids with aryl halides (Figure ). The proposed mechanism involves the reductive quenching of the excited PC by the carboxylate to yield an alkyl radical following decarboxylation. Closure of the photocatalytic cycle occurs by SET from the reduced PC to the Ni(I) species. Additionally, the PC is proposed to be responsible for the in situ generation of the active Ni(0) species through two SET reductions (Ered(Ni II /Ni 0 ) = -1.2 V vs SCE in DMF). As a result, the PC must be moderately photooxidizing as well as sufficiently reducing in the ground state.