Three New Metal Complexes with Imidazole-Containing Tripodal Ligands as Fluorophores for Nitroaromatics- and Ion-Selective Sensing.

Three new metal-organic complexes [Cd(TIPA)(suc)0.5(NO3)·1/2H2O]n (1), [Ni(TIPA)(tda)0.5(H2O)·1/4H2O]n (2) and [Cd(TIPA)(tda)0.5·11/2H2O] (3) were synthesized via rigid tripodal ligand tris(4-(1H-imidazol-1-yl)phenyl)amine (TIPA) and three dicarboxylic acids; either succinic acid (H2suc) or 2,5-thiophenedicarboxylic acid (H2tda). Crystallographic data for 1 - 3 reveal three-dimensional (3D) networks and channels in the structures. The structure of 2 is unique featuring an interpenetrating 2D network, 2D + 2D → 3D, with the two associated 2D networks existing in two opposite spiral channels. TGA plots exhibit a loss of mass corresponding to the loss of the solvated water molecules in the 100 - 200 °C temperature region and begin to lose additional fragments only at T > 300 °C revealing the robust nature of the 3D framework in the complexes. The metal-organic frameworks (MOFs) are screened for their potential application in the detection and removal of environmentally hazardous industrial pollutants. Fluorescence emission spectra for 1 and 2 show that the two MOFs are capable of sensing nitrobenzene (NB), with the nickel complex 2 exhibiting significantly higher sensing ability. Powder XRD data measured for 1 and 2 and those of NB-treated 1 and 2 show significant differences in their patterns, providing further support for the strong interaction between the MOF complexes and NB. The fluorescence emission observed for 1 is more effectively quenched by the presence of Fe3+ than the series of 17 other metal ions investigated. Complex 3 possesses some ability to adsorb inorganic pollutants.