Structural diversity in the self-assembly of various macrocyclic metallic tectons and 4,4′-biphenyldicarboxylic acid ligand

•Five new hexaazamacrocyclic Ni(II) complexes containing 4,4′-biphenyldicarboxylic acid.•Systematically structural studies of macrocyclic metallic tectons based coordination complexes.•Solvent/macrocycle-induced structural diversity in this supramolecular self-assembly.

Five new nickel(II) coordination complexes based on macrocyclic metallic tectons and 4,4′-biphenyldicarboxylic acid ligand, namely, [(NiL1)2(4,4′-bpdc)(CH3CN)2]⋅(ClO4)2⋅2CH3CN (1), {[(NiL1)(4,4′-bpdc)]⋅DMF⋅4H2O}n (2) and [(NiL1)2(4,4′-bpdc)(H2O)2][(NiL1)2(4,4′-bpdc)3]⋅14H2O (3), {(NiL2)(4,4′-bpdc)}n (4) and {[(NiL3)(4,4′-bpdc)]⋅8H2O}n (5) (L1 = 1,3,6,8,12,15-hexaazatricycloeicosane, L2 = 1,3,6,9,11,14-hexaazatricyclooctadecane and L3 = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradeca) have been synthesized and characterized by single-crystal X-ray diffraction. Each nickel(II) atom in complex 1 shows a [NiN5O] octahedral coordination geometry, where four nitrogen atoms from the hexaazamacrocycle ligand, one nitrogen atom from acetonitrile and one oxygen atom from the 4,4′-biphenyldicarboxylic acid ligand. However, all nickel(II) atoms in complexes 2–5 are six-coordinated with four nitrogen atoms from the hexaazamacrocycle ligand and two oxygen atoms from the 4,4′-biphenyldicarboxylic acid, resulting a [NiN4O2] octahedral coordination geometry. Complex 1 possesses an extended framework structure based on a discrete 0D fragment. Complex 2 contains a 3D supramolecular structure based on two 1D chains arraying uniformly in an ABAB manner. Hydrogen-bonded 1D chains in complex 3 rise to 3D frameworks with ABCABC fashion. Complex 4 features rare plywood structure based on 1D chain. Complex 5 has a 3D framework structure bearing 1D water hexamers chains. In addition, the solid states UV–Vis for complexes 1–5 have been investigated.

Graphical abstractSystematical studies of macrocyclic metallic tectons based coordination complexes are reported. The result shows solvent/macocycle-induced structural diversity in this supramolecular self-assembly.Figure optionsDownload full-size imageDownload as PowerPoint slide