Podands Based on 1,4,5,8‐Tetra‐Azaphenanthrene and Their Complexation With Ru2+

Summary. New podands, based on 1,4,5,8‐tetra‐azaphenanthrene, have been synthesized from 2‐chloro‐1,4,5,8‐tetra‐azaphenanthrene 3; when the anchoring group is a nitrogen atom, the corresponding podands are, however, unstable. When reacted with Ru2+in an ionizing solvent, podands tris(2‐(2‐(1,4,5,8‐tetra‐azaphenanthryloxy))ethyl)methane 4c and tri(2‐(2‐(1,4,5,8‐tetra‐azaphenanthryloxy))ethyl)trimesoate 9 give only polymeric complexes; in chloroform, complexation stops at bis‐chelation, giving two types of structures. The most intriguing is the twisted type (12, 13) where one of the chelating group has been inverted, giving rise to an unprecedented flattened Ru2+octahedron.