Toward Designed Assembly of Microporous Coordination Networks Constructed from Silver(I)−Hexamethylenetetramine Layers

Eight interesting microporous networks based on 2-D [Ag(mu(3)-hmt)] (hmt = hexamethylenetetramine) layers were obtained via rational synthetic strategies. Out of these products isolated and structurally characterized, six present a metal-to-hmt molar ratio of 1:1 and contain 2-D coordination layers assembled by 2-D Ag(I)-hmt networks with aromatic monocarboxylates, which are [Ag(mu(3)-hmt)(p-nba)].2.5H(2)O (1), [Ag(mu(3)-hmt)(m-nba)].2.5H(2)O (2), [Ag(mu(3)-hmt)(dnba)] (3), [Ag(mu(3)-hmt)(alpha-hna)](EtOH) (4), [Ag(mu(3)-hmt)(beta-hna)](EtOH) (5), and [Ag(mu(3)-hmt)(noa)](H(2)O)(EtOH) (6) (p-nba = 4-nitrobenzoate, m-nba = 3-nitrobenzoate, dnba = 3,5-dinitrobenzoate, alpha-hna = 1-hydroxy-2-naphthate, beta-hna = 3-hydroxy-2-naphthate, and noa = 2-naphthoxyacetate), and two present a metal-to-hmt molar ratio of 2:1 and contain 3-D microporous networks constructed from the 2-D Ag-hmt layers and linear dicarboxylates as molecular pillars, which are [Ag(2)(mu(3)-hmt)(2)(fa)].4H(2)O (7) and [Ag(2)(mu(3)-hmt)(2)(adp)].8H(2)O (8) (fa = fumarate and adp = adipate). The result shows that the pore sizes may be tuned with different carboxylates. Gas adsorption measurements were performed to confirm the microporosity of these coordination open frameworks.