Synthesis of Ce(IV) Heteroleptic Double‐Decker Complex with a New Helical Naphthalocyanine as a Potential Gearing Subunit

Jeevithra Dewi Subramaniam (1) , Yohei Hattori (1) , Fumio Asanoma (1) , Toshio Nishino (1) , Kazuma Yasuhara (1) , Colin Martin (1) , Gwénaël Rapenne (2, 3)

1 NAIST - Division of Materials Science, Nara Institute of Science and Technology
2 NAIST - Nara Institute of Science and Technology - Graduate School of Information Science
3 CEMES-GNS - Groupe NanoSciences

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.

Domaines: Chimie de coordination

Jeevithra Dewi Subramaniam, Yohei Hattori, Fumio Asanoma, Toshio Nishino, Kazuma Yasuhara, et al.. Synthesis of Ce(IV) Heteroleptic Double‐Decker Complex with a New Helical Naphthalocyanine as a Potential Gearing Subunit. Chemistry - A European Journal, inPress, ⟨10.1002/chem.202402470⟩. ⟨hal-04664141⟩