The photophysical properties of azobenzene–graphene quantum dot interfaces show enhanced photoinduced hole and energy transfer rates for the trans isomer, making it the acvite specie compared to the cis isomer.

An artificial leaf is a concept that not only replicates the processes taking place during natural photosynthesis but also provides a source of clean, renewable energy. One important part of such a device are molecules that stabilize the connection between the bioactive side and the electrode, as well as tune the electron transfer between them. In particular, nitrilotriacetic acid (NTA) derivatives used to form a self-assembly monolayer chemisorbed on a graphene monolayer can be seen as a prototypical interface that can be tuned to optimize the electron transfer. In the following work, interfaces with modifications of the metal nature, backbone saturation, and surface coverage density are presented by means of theoretical calculations. Effects of the type of the metal and the surface coverage density on the electronic properties are found to be key to tuning the electron transfer, while only a minor influence of backbone saturation is present. For all of the studied interfaces, the charge transfer flow goes from graphene to the SAM. We suggest that, in light of the strength of electron transfer, Co²⁺ should be considered as the preferred metal center for efficient charge transfer.

Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me₂Ga(µ-OCH(Me)CO₂R)]₂—were crucial for the heteroselectivity of [Me₂Ga(µ-OCH(Me)CO₂Me)]₂ in the ring-opening polymerization (ROP) of racemic lactide (rac-LA), we have investigated the effect of alkyl groups on the structure and catalytic properties of dialkylgallium alkoxides in the ROP of rac-LA. Therefore, we have isolated and characterized the rac-[R₂Ga(µ-OCH(Me)CO₂Me]₂ (R = Et (1), ⁱPr (2) and rac-[R₂Ga(µ-OCH(Me)C₅H₄N]₂ (R = Et (3), ⁱPr (4)) complexes, to demonstrate the effect of alkyl groups on the chiral recognition induced the formation of the respective homochiaral species—(R*,R*)-[R₂Ga(µ-OCH(Me)CO₂Me)]₂ and (R*,R*)-[R₂Ga(µ-OCH(Me)C₅H₄N]₂. Moreover, we have investigated the structure of (S,S)-[R₂Ga(µ-OCH(Me)CO₂Me]₂ (R = Et ((S,S)-1, R = ⁱPr ((S,S)-2,) and their catalytic activity in the ROP of rac-LA. With an increase in the bulkiness of alkyl substituents on gallium the following can be observed: (a) the tendency for the formation of homochiral complexes decreased, (b) the symmetry of homochiral (S,S)-[R₂Ga(µ-OCH(Me)CO₂Me]₂ (M = Me, Et (S,S)-1), ⁱPr (S,S)-2) changed, and both have resulted in (c) lower or no heteroselectivtity across these complexes in the ROP of rac-LA. Importantly, the results have confirmed the crucial role of the chiral-induced formation of homochiral asymmetric dimers on the heteroselectivity of dialkylgallium alkoxides in the ROP of rac-LA.