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 SO42−-bridge. Complex 4 shows a three-dimensional (3D) architecture and SO42− 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.

Six novel Ni(II)–fluconazole complexes have been hydro(solvo)thermally synthesized under similar conditions except different anions and solvents. Their structures span zero, one, two and three dimensions. Their different photoluminescence properties indicate that the introduction of different anions to metal–drug complexes can enhance or weaken the intra-ligand transitions of drug.Figure optionsDownload as PowerPoint slide