摘要:
IntroductionThe variety of structural features reported in new coordination polymers has attracted great attention in recent years.1–16The diversity of the structures and new topologies is attributed to the selection of metal centers as well as organic building blocks. The two-dimensional (2-D) layers and three-dimensional (3-D) networks are very attractive in their frameworks. Whereas several bilayer architectures have been reviewed by Zaworotko in which the bilayers were formed by partial interdigitation,17the double-layer coordination polymers formed from mutual-face-insertion have hardly been studied. The double-layer structures are apparently more complicated than single layers, and are assumed to have more intriguing structural features. We have recently demonstrated a new reaction route,viaan oxidation reactionmechanism, to synthesize novel coordination polymers which may not be accessible from known reaction routes.18aThe reported oxidation reaction route under hydrothermal conditions afforded a novel, mixed-valence Cu–Cu-bonded polymer with bridging iodine [(Cu2I)2+] mutual insertion network. It displayed interesting graphite-like layers and properties.18The terminal-iodine and isonicotinato (IN) ligand apparently played very important roles in the new structures, as did the square pyramidal copper metal centers. The square pyramidal copper metal centers with terminal iodine (Fig. 1) in a network structure may have a good tendency to form mutual-face-insertion double layers. This structural feature may be applied to tetrahedral metal centers such as zinc atoms. While the tetrahedral metal center exhibiting mutual insertion double-layerstructures has never been observed, due to the tetrahedral geometrical limitations (relative to the accessible pathways of the square pyramidal geometry), here we demonstrate such an example – [(IN)ZnI(INH)] (INH = protonated isonicotinato ligand),1– with an unprecedented tetrahedral zinc mutual-face-insertion double-layer metal–organic framework structure builtviaboth covalent and double-hydrogen bonding interactions.View of the square pyramidal copper open-framework with terminal iodine atoms.
ISSN:1466-8033
DOI:10.1039/b111353d
出版商:RSC
年代:2001
数据来源: RSC