Anion-directed assembly: Framework conversion in dimensionality and photoluminescence

Six novel Ni(II)-fluconazole complexes formulated as (C₁₃H₁₁N₆OF₂)₂Ni₂(NO₃)₂ (1), (C₁₃H₁₂N₆OF₂)₂Ni(NO₃)₂·H₂O (2), (C₁₃H₁₂N₆OF₂)Ni(SO₄)(DMF)₂(H₂O) (3), (C₁₃H₁₂N₆OF₂)₂Ni(H₂O)₂(SO₄)·4H₂O (4), (C₁₃H₁₂N₆OF₂)₂NiCl₂·2(CH₃OH) (5), (C₁₃H₁₂N₆OF₂)₄Ni₂ (MoO₄)₂·6H₂O (6) have been hydrothermally or solvothermally synthesized under similar conditions except different anions and solvents. They are structurally characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Complex 1 is a molecular binuclear nickel cluster. Complex 2 exhibits a one-dimensional (1D) chain linked by double-stranded fluconazole-bridge. Complex 3 shows a novel 1D chain linked by double-stranded fluconazole-bridge and double-stranded SO₄^2--bridge. Complex 4 shows a three-dimensional (3D) architecture and SO₄^2- anions occupy the cavity. Complex 5 exhibits a two-dimensional (2D) structure constructed by alternating left- and right-handed helices. Complex 6 exhibits a 3D architecture, in which the 2D layers are pillared by {MoO₄} tetrahedra. Complex 2 can be irreversibly converted to complex 1 in the presence of DMF (N,N′-dimethyllformamide). Complexes 1, 3 and 6 show antiferromagnetic interactions between the nickel (II) ions The photoluminescence properties of the six complexes indicated that the introduction of different anions can enhance or weaken the intra-ligand transitions of fluconazole.