A Family of Metal–Organic Frameworks with a New Chair-Conformation Resorcin[4]arene-Based Ligand: Selective Luminescent Sensing of Amine and Aldehyde Vapors, and Solvent-Mediated Structural Transformations

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• 作者：Hang Zhang ; Jin Yang ; Ying-Ying Liu ; Shuyan Song ; Jian-Fang Ma
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：16
• 期：6
• 页码：3244-3255
• 全文大小：1020K
• 年卷期：0
• ISSN：1528-7505

文摘

By utilizing a new chair-conformation resorcin[4]arene-based octacarboxylate ligand, four functional metal–organic frameworks (MOFs), namely, [(CH₃)₂NH₂]₄[Cd₂(L)]·4H₂O (1), [(CH₃)₂NH₂]₄[Zn₂(L)]·2DMF·6H₂O (2), [(CH₃)₂NH₂]₄[Co₂(L)]·2DMF·4H₂O (3), and [(CH₃)₂NH₂]₂[Co₃(L)(H₂O)₁₂] (4) (H₈L = 2,8,14,20-tetra-methylphenyl-4,6,10,12,16,18,22,24-octa-carboxymethoxy-resorcin[4]arene and DMF = N,N-dimethylformamide), were solvothermally synthesized and structurally characterized. In 1, each L^8– anion bridges eight Cd(II) atoms to give a three-dimensional (3D) (4,8)-connected (4⁶)(4¹².6¹⁰.8⁶) framework. In isostructural 2 and 3, each L^8– anion links eight adjacent Zn(II) or Co(II) atoms to yield a 3D (4,8)-connected (4⁶)(4¹¹.6¹².8⁵) net. In 4, each L^8– anion only bridges four Co(II) atoms by using its four carboxylates each in a monodentate coordination mode to generate an infinite one-dimensional (1D) chain. Remarkably, the highly selective luminescent sensing of amine and aldehyde vapors was studied for 1 and 2 as fluorescent sensors. Importantly, a solvent-induced structural transformation from the 1D chain to the 3D porous framework between 3 and 4 was also investigated in detail.