RESUMO
This paper describes the synthesis of a cerium(IV)-based molecular gear composed of a thioether functionalized phthalocyanine anchoring ligand, and a helical naphthalocyanine rotating cogwheel functionalized with four carbazoles. The naphthalocyanine ligand 9 was obtained after eleven steps (overall yield of 0.2 %) as a mixture of three geometrical isomers, two of which are chiral and exhibit high levels of steric hindrance, as shown by DFT calculations. Their attributions have been made using 1H-NMR based on their different symmetry groups. The ratio of isomers was also determined and the prochiral C4h naphthalocyanine shown to be the major compound (55 %). Its heteroleptic complexation with cerium (IV) and the anchoring phthalocyanine ligand 10 gave the targeted molecular gear in a 16 % yield.
RESUMO
Phthalocyanines and their double-decker complexes are interesting in designing rotative molecular machines, which are crucial for the development of molecular motors and gears. This study explores the design and synthesis of three bulky phthalocyanine ligands functionalized at the α-positions with phenothiazine or carbazole fragments, aiming to investigate dynamic rotational motions in these sterically hindered molecular complexes. Homoleptic and heteroleptic double-decker complexes were synthesized through the complexation of these ligands with Ce(IV). Notably, CeIV(Pc2)2 and CeIV(Pc3)2, both homoleptic complexes, exhibited blocked rotational motions even at high temperatures. The heteroleptic CeIV(Pc)(Pc3) complex, designed to lower symmetry, demonstrated switchable rotation along the pseudo-C4 symmetry axis upon heating the solution. Variable-temperature 1H-NMR studies revealed distinct dynamic behaviors in these complexes. This study provides insights into the rotational dynamics of sterically hindered double-decker complexes, paving the way for their use in the field of rotative molecular machines.