Stitching 2D Polymeric Layers into Flexible 3D Metal–Organic Frameworks via a Sequential Self-Assembly Approach

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• 作者：Hao Zhang ; Tianlu Sheng ; Shengmin Hu ; Chao Zhuo ; Haoran Li ; Ruibiao Fu ; Yuehong Wen ; Xintao Wu
• 刊名：Crystal Growth & Design
• 出版年：2016
• 出版时间：June 1, 2016
• 年：2016
• 卷：16
• 期：6
• 页码：3154-3162
• 全文大小：600K
• 年卷期：0
• ISSN：1528-7505

文摘

Two-dimensional (2D) coordination polymer [Zn(ATZ)₂]_n (HATZ = 5-amino-1H-tetrazole) featuring a 2D + 2D → 2D pillar-layer array was synthesized, wherein two honeycomb-shaped Zn(ATZ)_1.5 sublayers can be stitched together by dicarboxylate bridging linkers of varied length and type to generate 4 three-dimensional (3D) isoreticular noninterperpentrated frameworks under solvothermal conditions. The interpenetration behavior may be constrained to some extent by the pillar length because a 3D twofold interpenetrated architecture was obtained with a longer ligand using a similar process. The pillar-exchange process enabled the facile synthesis of a family of isoreticular metal–organic framework structures with different flexibilities and interpenetration behaviors through the judicious choice of the type and size of the pillar units. Thermal analysis indicated that [Zn(ATZ)₂]_n also possesses excellent thermostability at a high decomposition temperature up to 356 °C. The kinetic parameters of its exothermic process were studied by Kissinger’s and Ozawa–Doyle’s methods. Furthermore, its luminescent properties at room temperature were also studied in detail.