Two hexaarylbenzenes having six pyridine substituents (LH and LM) were prepared and six corresponding coordination complexes with copper(i) chloride were synthesized. Monomeric complexes (1, 2a and 2b) and 1D coordination polymers (3, 4 and 5) were synthesized via the judicious concentration control of copper(i) ions and characterized fully by X-ray crystal analysis. The binding modes of the ligands to copper(i) ions in the coordination polymers were dependent on steric effects and solvents to determine the morphology of the coordination polymers. More interestingly, dynamic behaviours of the monomeric complexes (1, 2a and 2b) in the solution phase were studied to show potential applications of molecular machines with fluxional motions.