The metallophotoredox catalyst, [Ir{dF(CF3)ppy}2(dtbpy)]PF6, was prepared in two steps from IrCl3 via the method of Lowry et al. The sp 3 -sp 3 metallophotoredox coupling reactions were performed in 25 ml reaction tubes (Sigma Aldrich, part no. Z515981. Irradiation was from two LED emitters (Mouser, part no. LZ1-10UB00-00U8, 405 nm peak output, 1050 mW radiant flux) mounted on anodised aluminium heatsinks (Mouser, part no. 984-ATSEU-077B-C6-R0) at opposite sides of the reaction tube at a distance of approximately 1 cm from the wall of the reaction tube. The LED and reactor assembly was cooled with a fan during operation. Nickel mediated decarboxylative alkyl-alkyl cross couplings of N-hydroxyphthalamide esters with organozinc reagents were performed via the method of Qin et al. 4-(Pent-4-eneyloxy)-4′cyanobiphenyl was prepared as reported previously. 5-Cyclohexylpentan-1-ol was prepared via the method of Perez et al. in > 95 % yield using lithium aluminium hydride in THF. 6-Cyclohexylhexan-1-ol was prepared according to Liu et al. THF and dichloromethane were purchased from Fisher Scientific UK and were dried via passage over activated alumina.