Supramolecular Architectures of Macrocyclic Nickel(II) Complexes with Defined Structures of Cis and Trans Configurations

Two isomers of [Ni( α - rac -L)](ClO 4 ) 2 and [Ni( β ‘- rac -L)](ClO 4 ) 2 were prepared, and their configurations and reaction properties were investigated (L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Reactions of [Ni( α - rac -L)](ClO 4 ) 2 isomer with HBDC -, BDC 2-, and pyca - ligands give six-coordinated cis -nickel(II) complexes of cis -[Ni( f-rac -L)(HBDC)](ClO 4 ) 1, cis -{[Ni( f-rac -L)] 2 (BDC)(H 2 O)}(H 2 O) 2 (ClO 4 ) 2 2, and cis -[Ni( f-rac -L)(pyca)](ClO 4 ) 4, where BDC = trans -butene dicarboxylate and pyca = 4-pyridinecarboxylate. Reactions of [Ni( β ‘- rac -L)](ClO 4 ) 2 isomer with HBDC - and pyca - lead to six-coordinated trans -nickel(II) complexes of { trans -[Ni( meso -L)(BDC)](H 2 BDC)} n 3 and trans -[Ni( meso -L)(pyca) 2 ] (H 2 O) 2 5 . Single-crystal X-ray diffraction analyses reveal that 1 and 4 form one-dimensional (1D) zigzag chains via the intermolecular hydrogen bonds, 2 is a dimer of two [NiL] 2+ units bridged by one BDC 2- anion, 3 forms a two-dimensional layer structure of BDCH 2 molecules hydrogen bonded with 1D chains of [Ni( meso -L)(BDC)] n, and 5 is an extended hydrogen-bonded three-dimensional network.