A new rigid benzene‐bridged macrotricyclic ligand

A macrotricyclic ligand composed of two benzene rings connected by four 2,2′‐oxydiphenoxide bridges ( 2 ) has been prepared by treating 1,2,4,5‐tetrakis[2‐(2‐hydroxyphenoxy)phenoxymethyl]benzene with 1,2,4,5‐tetrakis(bromomethyl)benzene in acetonitrile in the presence of potassium carbonate. Ligand 2 is of interest because of its similarity to macrocycle 1 which interacts strongly with cesium ions. The proposed more direct route of treating an excess of 2,2′‐oxydiphenol with 1,2,4,5‐tetrakis(bromomethyl)benzene to prepare 2 did not give the desired macrocycle but gave bis(tribenzo‐11‐crown‐3) ( 8 ). An X‐ray crystal structure study of 2 showed that the benzene rings which are linked by the four 2,2′‐oxydiphenoxide bridges are connected in a nonsymmetric pattern. The structure of 8 was also determined using X‐ray diffraction methods, and is reported.