Yttrium‐Catalyzed Synthesis of Bipyridine‐Functionalized AB‐Block Copolymers: Micellar Support for Photocatalytic Active Rhenium‐Complexes

Herein, ortho ‐methylated bipyridines are introduced as initiators in 2‐aminoalkoxy‐bis (phenolate) yttrium complexes. For this C−H bond activation (ONOO) t Bu 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 metal‐mediated 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 ).