摘要：

As self-assembly of the supramolecular architectures of coordination polymers is influenced by the many different factors, it is usually difficult to predict the structure of the product of self-assembly. As sequel work of our previous reports on coordination polymers with variable cavities or channels^[1], we attempt to develop rational synthesis of desired molecular architectures and describe our design and construction of supramolecular architectures based on Ag-HMT (hmt=hexamethylenetetramine) nets. HMT is a potential tetradendate ligand, and Ag¹ is flexible in coordination. We obtained a number of Ag-HMT nets in different dimension-alities, some of the Ag-HMT networks are stable, and may be further tailored to generate designed 3-D molecular architectures^[2]. In particular, the lateral positions of the hexagonal 2-D[Ag(μ₃-hmt)X] nets are occupied by small and labile ligands (X=NO₃^- or NO₂^-, which are align-ed in an alternative up/down fashion. The lateral ligands may be replaced by other functional ligands to provide new routes (see scheme below) in organising the 2-D layers into 3-D nets via linear dicarboxylates as molecular pillars or interlayer intercalation between the lateral aromatic mono-carboxylates, giving the designed 3-D molecular architectures with variable porous sizes. In this report, we will show a series of 3-D molecular architectures based on the hexagonal nets. On the other hand, when non-linear dicarboxylates are used, some other 3-D polymeric architectures can be isolated, including some of nanometer-sized channels. Study of gas absorption of the pore materials is under progress.

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