The synthesis and characterization of giant Calixarenes

Vincent Guérineau (1) , Marion Rollet (2) , Stéphane Viel (2) , Bénédicte Lepoittevin (3, 4) , Ludovic Costa (4) , Pascale Saint-Aguet (5) , Regis Laurent (6) , Philippe Roger (4) , Didier Gigmes (2) , Cyril Martini (4) , Vincent Huc (4)

1 ICSN - Institut de Chimie des Substances Naturelles
2 ICR - Institut de Chimie Radicalaire
3 LCMT - Laboratoire de chimie moléculaire et thioorganique
4 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay
5 ICT - Institut de Chimie de Toulouse
6 LCC - Laboratoire de chimie de coordination

Calixarenes are cyclic oligomers obtained by condensation of suitable p-functionalised phenols with formaldehyde, usually allowing for the synthesis of the well known small calixarenes (including up to eight phenolic subunits). We report here the discovery of much larger members of this family, exhibiting sizes up to 90 phenolic subunits: the giant calixarenes. These macrocycles are obtained according to simple, easily scalable processes, in yields up to 65%. We show that the formation of these giant macrocycles is favored by an oxygen-containing-group at the para-position of the starting phenol, high concentrations of heavy alkaline bases (rubidium or cesium hydroxides) and long reaction times. A mechanism is proposed to rationalize these observations. These giant macrocycles can also be obtained in the quasi-solid state, opening interesting perspectives in the field of calixarenes chemistry. Along with their intrinsic fundamental interest, these objects are also opening interesting applicative potentialities.

Domaines: Chimie

Vincent Guérineau, Marion Rollet, Stéphane Viel, Bénédicte Lepoittevin, Ludovic Costa, et al.. The synthesis and characterization of giant Calixarenes. Nature Communications, 2019, 10 (1), pp.113. ⟨10.1038/s41467-018-07751-4⟩. ⟨hal-01998267⟩