Shorter Alkyl Chains Enhance Molecular Diffusion and Electron Transfer Kinetics between Photosensitisers and Catalysts in CO₂-Reducing Photocatalytic Liposomes

Covalent functionalisation with alkyl tails is a common method for supporting molecular catalysts and photosensitisers onto lipid bilayers, but the influence of the alkyl chain length on the photocatalytic performances of the resulting liposomes is not well understood. In this work, we first prepared a series of rhenium-based CO₂-reduction catalysts [Re(4,4’-(C_nH_2n+1)₂-bpy)(CO)₃Cl] (ReC_n; 4,4’-(C_nH_2n+1)₂-bpy=4,4’-dialkyl-2,2’-bipyridine) and ruthenium-based photosensitisers [Ru(bpy)₂(4,4’-(C_nH_2n+1)₂-bpy)](PF₆)₂ (RuC_n) with different alkyl chain lengths (n=0, 9, 12, 15, 17, and 19). We then prepared a series of PEGylated DPPC liposomes containing RuC_n and ReC_n, hereafter noted C_n, to perform photocatalytic CO₂ reduction in the presence of sodium ascorbate. The photocatalytic performance of the C_n liposomes was found to depend on the alkyl tail length, as the turnover number for CO (TON) was inversely correlated to the alkyl chain length, with a more than fivefold higher CO production (TON=14.5) for the C₉ liposomes, compared to C₁₉ (TON=2.8). Based on immobilisation efficiency quantification, diffusion kinetics, and time-resolved spectroscopy, we identified the main reason for this trend: two types of membrane-bound RuC_n species can be found in the membrane, either deeply buried in the bilayer and diffusing slowly, or less buried with much faster diffusion kinetics. Our data suggest that the higher photocatalytic performance of the C₉ system is due to the higher fraction of the more mobile and less buried molecular species, which leads to enhanced electron transfer kinetics between RuC₉ and ReC₉.