Herein, ortho-methylated bipyridines are introduced as initiators in 2-aminoalkoxy-bis (phenolate) yttrium complexes. For this CÀH bond activation (ONOO) tBu Y(CH 2 TMS)(thf) (1) (TMS = trimethylsilyl) is reacted with the respective bipyridine to obtain complexes (ONOO) tBu Y(6-Me 2 bpy) (2) and (ONOO) tBu Y(6-Mebpy) (3). Both complexes were tested first in rare-earth metalmediated group-transfer polymerization of 2-vinylpridine (2VP). Complex 3 was further tested in block copolymerizations of 2VP and diethyl vinylphosphonate. The obtained initiator-P2VP-PDEVP-block copolymers can selectively react with Re(CO) 5 Cl at their bipyridine end-group. The obtained rhenium functionalized block copolymers are able to self-assemble to unimodal micelles in water, representing a possible carrier for hydrophobic metal containing complexes into cells. Furthermore, the Re-block copolymers sustain activity in the photocatalytic homogeneous CO 2 reduction and their performance exceed the catalytic activity of the analogue polymer-free system [Re(CO) 3 (6-Mebpy)Cl] (4). . CÀH bond activation of 1 with 6-Me 2 bpy and 6-Mebpy to obtain bipyridine-functionalized yttrium bis (phenolate) complexes 2 and 3.

A significant decrease in the amount of the sacrificial electron donor triethanolamine (TEOA) required for the homogeneous photocatalytic reduction of CO2 using rhenium-based catalytic systems can be achieved by adding small quantities of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) to the reaction mixture. The turnover numbers (TONs) and frequencies (TOFs) measured for the reactions described herein are even higher than those observed in reaction mixtures containing high concentrations of TEOA. Furthermore, replacing TEOA with DBU in the solutions of Re(i)/Ru(ii) mixed catalytic systems leads to a doubling of the values of TON and TOF.

The one‐electron‐reduced (OER) species of rhenium‐based catalysts in the homogeneous photocatalytic reduction of CO2 represents the starting point of light‐induced deactivation processes, which lead to low catalyst activity and productivity. Herein, we report the suppression of these processes using pulsed light. Experimental parameters to avoid the irradiation of the OER species were estimated, leading us to conclude that pulse lengths shorter than 1 ns and repetition rates lower than 33 Hz should be employed. [Re(bpy)(CO)3X] (bpy=2,2′‐bipyridine; X=Cl (1), Br (3)) catalysts were employed in pulsed irradiation experiments using different light sources, pulse lengths and repetition rates. Pulsed irradiation experiments using LEDs revealed that a minimum average photon flux is necessary to enable CO2 conversion. Furthermore, pulsed laser light with a 10 ns pulse length partially prevented lightinduced deactivation processes, whereas efficient suppression was achieved using a 30 ps pulse length.