Porous Solids by Design: |Zn(4,4'-hpy_2(SiF_6)}_n-xDMF, a Single Framework Octahedral Coordination Polymer with Large Square Channels

摘要

The concept of crystal engineering has in recent years provided numerous examples of rationally designed one (ID), two (2D). and three-dimensional (3D) polymeric structure-;. Of particular potential interest to inclusion ehemistr) are 2D and 3D coordination polymers which, in principle a; '.cast, can be designed to haw very specific pore size and type, in such a context. there already exist examples of 2D square and hexagonal honeycomb grids generated from memlions in square-planar or trigonal environments, respectively, coordinated to linear bifunctional ligands such as 4.4'-btpyridine or pyrazines. Furthermore. 3D ddiamondoid coordination polymers based upon tetrahedrai or S_4 coordination environments have beer, generated by cither coordinate covalent bonus or hydrogen bonding. However, given the ubiquity of octahedral metal environments, it is somewhat surprising that simple 3D octahedral polymers remain largely unexplored. Indeed, to our knowledge μ-cyano polymers such as Fe_4~(III)[Fe~(II)(CN)_6]_3. Prussian Blue, the poorly characterized [Cd(CN)_2 (qiunoxalinel]_n and trinh interpenetrated [Cd(pyrazine){Ag_2CN)_3}{Ag(CN)_2] represent the only examples of such structures. Recenth a coordination polymer from silver ions and pyrazine was synthesized and structurally characterized. In this contribution we detail a potentially general strategy for generatior of such polvmers.