Topology‐Controlled Metallamacrocyclic Assemblies Containing Ni²⁺ and Alkali Metal Ions with Catechol‐Scaffolding Aroylbis(N,N‐Diethylthiourea)

Self‐assemblies between H 2 L cat ligand and the mixture of Ni(OAc) 2 · 4 H 2 O and alkaline metal chlorides MCl (M = K, Rb, Cs) in MeOH/H 2 O can form metallacoronate and metallacryptate complexes. The topology of the metal complexes strongly depends on the ionic radii of the alkali metal ions. The small K + ion favors to form the {2}‐metallacoronate [K ⊂ Ni 2 (L cat ) 2 ] + , while the medium size Rb + ion can form both {2}‐metallacoronate [Rb ⊂ Ni 2 (L cat ) 2 ] + and {3}‐metallacoronate [Rb ⊂ Ni 3 (L cat ) 3 ] + . The large Cs + ion exclusively adopts the {3}‐metallacoronate [Cs ⊂ Ni 3 (L cat ) 3 ] + . In contrast, the metallacryptate complexes consistently display [M ⊂ Ni 2 (L cat ) 3 ] − (M = K, Rb, Cs) architecture, regardless of the size of the alkali metal ions.