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

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• 作者：Zhenzhen Shi ; Zhaorui Pan ; Hailang Jia ; Shuguang Chen ; Ling Qin ; Hegen Zheng
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：May 4, 2016
• 年：2016
• 卷：16
• 期：5
• 页码：2747-2755
• 全文大小：763K
• 年卷期：0
• ISSN：1528-7505

文摘

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 → 2D) with the sql topology that are further formed into a three-dimensional (3D) supramolecular structure by interlayer π···π 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 (4¹⁴·8)(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.