Robust 2D Coordination Networks from a Two-Step Assembly Process with Predesigned Silver Cyclic Dimers and Hexamethylenetetramine

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• 作者：Gema Dur谩 ; M. Carmen Carri贸n ; F茅lix A. Jal贸n ; Blanca R. Manzano ; Ana M. Rodr铆guez ; Kurt Mereiter
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：July 1, 2015
• 年：2015
• 卷：15
• 期：7
• 页码：3321-3331
• 全文大小：565K
• ISSN：1528-7505

文摘

A two-step self-assembly methodology has been used to obtain 2D coordination polymers with an egg-crate structure of trigonal symmetry and space group R3虆m. The polymers have the molecular formula [Ag₃(L¹)₃(hmt)]X₃ (L¹ = bis(pyrazol-1-yl)(pyridin-4-yl)methane; hmt = hexamethylenetetramine; X = BF₄, ClO₄, PF₆). In the first step, the previously reported box-like cyclic dimers [Ag L¹]₂X₂, in which the ligands L¹ are in a head-to-tail disposition, were obtained and these were subsequently reacted with the base hexamethylenetetramine to form Ag鈥揘(hmt) bonds. The dimers act as linear connectors and the bases as triconnected nodes to give slightly undulating hexagons that form honeycomb sheets. The sheets follow an ABCABC stacking arrangement along [001] so that between them two types of large cavities arise which are occupied by disordered solvent, e.g., DMF inherited from synthesis. The anions, which participate in the formation of the cavities, interact with the sheets through hydrogen bonds. The polymers can be activated by removing the solvents without collapsing, which enabled an evaluation of these materials for use as gas adsorption, anion exchange, and proton capture systems.