Ligand-Directed Construction of Zn(II) Complexes from Zero-Dimensional Metallomacrocycle to One-, Two-, and Three-Dimensional Coordination Polymers Based on N-Donor and β-Diketone Bifunctional Ligands

Six new complexes [Zri(2)(L-1)(4)]center dot 2H(2)O center dot DMF (1), [Zn-2(L-2)4](3)center dot 13H(2)O (2), [Zn-1.5(L-3)(3)](2) (3), Zn(L-4)(2)center dot 2H(2)O (4), Zn(L-5)(2)center dot 2CHCl(3) (5), and [Zn(L-6)(2)](2) (6) (where HL1 = 1-(4-(1H-imidazol-1-yl)phenyl)butane-1,3-dione, HL2 = 1-(4-(1H-benzimidazol-1-yl)phenyl)butane-1,3-dione, HL3 = 1-(4-(1H-pyrazol-1-yl)phenyl)butane-1,3-dione, HL4 = 1-(3-(1H-imidazol-1-yl)phenyl)butane-1,3-dione, HL6 = 1-(3-(1H-benzimidazol-1-yl)phenyl)butane-1,3-dione and HL6 = 1-(3-(1H-pyrazol-1-yl)phenyl)butane-1,3-dione) have been synthesized by the reaction of the bifunctional ligands and Zn(II) salts under similar experimental conditions. Structural analyses show that the ligands act as a tridentate and bind to two Zn(II) ions as a two-connected linker, generating a variety of geometries from discrete binuclear [2 + 2] metallomacrocycles (3 and 6) to a one-dimensional looped-chain coordination polymer (4) and twodimensional (4,4) network (5) as well as three-dimensional frameworks with lvt (1) and Nb0 (2) topologies. The results demonstrate that the diverse structures are strongly dependent on the ligand geometries, due to the free rotation via the C-N/C-C bonds as well as the various coordinated sites of N-donor allowing the semirigidity ligands to take on appropriate conformations.