Zn(II)/Cd(II) Terephthalate Coordination Polymers Incorporating Bi-, Tri-, and Tetratopic Phenylamine Derivatives: Crystal Structures and Photoluminescent Properties

Using reticular chemistry allowed the design and construction of four novel Zn(II)/Cd(II) coordination polymers, [Zn (BTPA) (TPA)]center dot H2O}n (1), {[Zn(TTPA) (TPA)]center dot H2O}(n) (2); {[Cd-2(TTPA)(2)(TPA)(2)(DMF)].2H(2)O}(n) (3), and {[Cd(TTPBDA)-(TPA)(0.5)center dot DMF center dot H2O}(n) (4). They were successfully synthesized from bi-, tri-, and tetratopic phenylamine derivatives (BTPA = bis(4-:(1H-1,2,4-triazol-1-yl)phenyl)amine, TTPA = tris(4-(1H-1,2,4-triazol-1-yl)phenyl) amine, TTPBDA = N-4,N-4,N-4',N-4'-tetrakis (4-(1H-1,2,4-triazol-1-yl)phenyl)-(1,1'-biphenyl)-4,4'-diamine) incorporating a linear terephthalic acid (H(2)TPA) ligand and Zn(II)/cd(II) nitrate salts. These transparent crystals present gradually increasing dimensionality and complexity upon extension of the denticity of the phenylamine organic building blocks, as clearly supported by single-crystal X-ray analysis, infrared spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. Complex 1 shows two-dimensional (2D) threefold -interpenetrating layers (2D + 2D -> 2D) with the sql topology that are further formed into a three-dimensional (3D) supramolecular structure by interlayer pi center dot center dot center dot pi stacking and hydrogen-bonding interactions. Complex 2 displays 2D layers with the hcb topology that are further assembled into a 3D fourfold -interpenetrating supramolecular framework with the 3,4,4T25 topology by hydrogen-bonding interactions. Complex 3 possesses a fourfold -interpenetrating 3D (3,4,5)-connected architecture with the 3,4,5T86 topology. Complex 4 features an interesting and unusual new self-penetrating (4,6) -connected 3D topological network with the point symbol of (4(14). 8) (66), which contains a fourfold-interpenetrated 3D dia network linked by TPA(2-) ligands. The results suggest that these diverse coordination networks mainly can be adjusted by the number of 1,2,4-triazole substituents on the aniline backbones and the coordination geometries of the metal ions. Furthermore, the photoluminescence spectra and emission decay lifetimes of complexes 1-4 were examined.