Polymeric Luminescent Zn(II) and Cd(II) Dicarboxylates Decorated by Oxime Ligands: Tuning the Dimensionality and Adsorption Capacity

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• 作者：Lilia Croitor ; Eduard B. Coropceanu ; Art毛m E. Masunov ; Hector J. Rivera-Jacquez ; Anatolii V. Siminel ; Vyacheslav I. Zelentsov ; Tatiana Ya. Datsko ; Marina S. Fonari
• 刊名：Crystal Growth & Design
• 出版年：2014
• 出版时间：August 6, 2014
• 年：2014
• 卷：14
• 期：8
• 页码：3935-3948
• 全文大小：1002K
• ISSN：1528-7505

文摘

Ten Zn(II) and Cd(II) metal鈥搊rganic materials were synthesized and studied by the X-ray method. Among these 10 structures, two represent binuclear clusters, and two are one-dimensional (1D) coordination polymers, while five are laminar two-dimensional (2D) solids and one is the three-dimensional (3D) framework. The investigation has been aimed at rational design of coordination polymers decorated by oxime ligands to increase the accessible adsorption area in these newly synthesized solids. The ligands used include three aliphatic dicarboxylic acids, HOOC-(CH<sub>2sub>)<sub>nsub>-COOH [n = 1, 2, 4 corresponding to malonic (H<sub>2sub>mal), succinic (H<sub>2sub>suc), and adipic (H<sub>2sub>adi) acids], and three neutral oxime ligands [pyridine-2-aldoxime (2-pyao), pyridine-4-aldoxime (4-pyao), and 1,2-cyclohexanedionedioxime (Niox)]. These novel hybrid solids with the compositions [Zn<sub>2sub>(suc)<sub>2sub>(2-pyao)<sub>4sub>]路2H<sub>2sub>O 1, [Cd<sub>2sub>(suc)(2-pyao)<sub>4sub>(H<sub>2sub>O)<sub>2sub>][BF<sub>4sub>]<sub>2sub> 2, [Cd(suc)(2-pyao)<sub>2sub>]<sub>nsub> 3, [Zn(mal)(4-pyao)(H<sub>2sub>O)]<sub>nsub> 4, [Cd(mal)(4-pyao)(H<sub>2sub>O)]<sub>nsub> 5, [Zn(suc)(4-pyao)]<sub>nsub> 6, [Zn(adi)(4-pyao)<sub>2sub>]<sub>nsub> 7, {[Cd(adi)(4-pyao)<sub>2sub>]路dmf}<sub>nsub> 8, [Zn(adi)(Niox)]<sub>nsub>9, and [Cd(adi)(Niox)]<sub>nsub> 10 [dmf 鈥?N,N鈥?dimethylformamide] demonstrate a variable class of coordination supramolecular architectures dictated by the distinctions in the metals鈥?and oxime ligands鈥?coordination capacities and preferences, and length and flexibility of the dicarboxylic linkers. The discrete aggregates 1 and 2 differ by the components鈥?ratio and conformation of the bridging succinate anion; compounds 3 and 7 are 1D arrays, and compounds 4, 5, 6, 8, and 9 represent 2D layers of different topologies. Compound 10 is a 3D grid afforded by the concerted contribution of the longest in this series adipate anion, and the bigger atomic radius Cd(II) vs. Zn(II). The adsorptive properties of 7 and 9 are reported. For the laminar solid 9, the quantum chemical simulations of the adsorption capacity are in line with the experimental results. All new materials reveal dual green-blue wavelength emission in the solid state.