Construction of Various Supramolecules by π−π Interactions: Self-Assembly of Nickel(II) Macrocyclic Complexes Containing Pyridine Pendant Arms with Bidentate Ligands

Abstract

The supramolecular compounds, [Ni(C20H32N8)(en)](ClO4)2 · 2 H2O (1), [Ni(C20H32N8)(isonicotinate)2] (2), and [Ni(C20H32N8)(BQDC)] · 3 H2O (3), have been constructed by the self-assembly of a nickel(II) macrocyclic complex containing pyridyl pendant rings, [Ni(C20H32N8)](ClO4)2 · 2 H2O, with ethylenediamine (hereafter noted en), isonicotinic acid, and potassium 2,2′-biquinoline-4,4′-dicarboxylate, (K2BQDC · 3 H2O), respectively, in MeCN/H2O. The X-ray crystal structure of 1 indicates that one en coordinates a nickel(II) macrocyclic complex to form a folded macrocyclic complex, which ends up with a stacking dimer via C−H···π and offset face-to-face π−π interactions between the pyridine pendant groups. The X-ray crystal structure of 2 indicates that two isonicotinate ions coordinate a nickel(II) macrocyclic complex at the axial positions and the pyridine groups of the coordinated isonicotinates are involved in offset face-to-face π−π interactions, which gives rise to a 1D chain. The 1D chains are linked together via the offset face-to-face π−π interactions between the pyridine groups of the macrocycle to generate a 2D network. The X-ray crystal structure of 3 indicates that each BQDC2− ion coordinates two nickel(II) macrocyclic complexes and each nickel(II) macrocyclic unit binds two BQDC2− ions at the axial positions to form a 1D chain. The 1D chains experience the intramolecular hydrogen bonding as well as the interchain offset face-to-face π−π interactions between the pyridyl pendant rings of the macrocycle and the BQDC2− ions, which gives rise to a 2D sheet. Between the 2D sheets herringbone π−π interactions exist, which results in a 3D framework.