Preferential Formation of Three‐layered Host–Guest Complexes of a Planar Dinuclear Metallohost with Alkali Metal Ions.

We synthesized a planar macrocyclic dinuclear nickel(II) metallohost from the corresponding macrocyclic imine ligand containing two N2O2 chelate coordination sites and an O6 cation binding site like 18‐crown‐6 as well as peripheral hexyl groups. Due to the lipophilic nature of the hexyl groups, the metallohost was soluble in less polar media where its interaction with alkali metal ions was enhanced. The binding studies by NMR spectroscopy clearly showed its strong tendency to form multi‐layered structures. The metallohost formed 2 : 1 and 1 : 1 (host/guest) complexes with Na+ with the two‐step binding constants of log<italic>K</italic>1=6.6 and log<italic>K</italic>2=3.0. In contrast, its complexation with larger alkali metal ions (K+, Rb+, Cs+) preferentially gave 3 : 2 (host/guest) complexes when 2/3 equiv. of the guest was present. The three‐layered structures of these 3 : 2 complexes were well characterized by mass spectrometry and 2D COSY/ROESY experiments as well as DFT calculations, elucidating their unique structural feature with three chemically different environments due to the oppositely curved two [Ni(saloph)] moieties of the metallohost. Therefore, the three‐layered structures were preferentially formed when larger alkali metal ions (K+, Rb+, Cs+) were complexed with the metallohost. [ABSTRACT FROM AUTHOR]