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)]·H2O}n (1), {[Zn(TTPA)(TPA)]·H2O}n (2), {[Cd2(TTPA)2(TPA)2(DMF)]·2H2O}n (3), and {[Cd(TTPBDA)(TPA)]0.5·DMF·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 = N4,N4,N4′,N4′-tetrakis(4-(1H-1,2,4-triazol-1-yl)phenyl)-(1,1′-biphenyl)-4,4′-diamine) incorporating a linear terephthalic acid (H2TPA) 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...