Template Assembly of Polyiodide Networks at Complexed Metal Cations: Synthesis and Structures of [Pd2 Cl2 ([18]aneN2 S4 )]1.5 I5 (I3 )2 and [K([15]aneO5 )2 ]I9.

The cations [Pd2 Cl2 L]2+ and [KL2'+ (L = [18]aneN2 S4 , L' =[15]aneO5 ) have been used as templates for the synthesis of unique three-dimensional polyiodide networks. The metal cations in [Pd2 Cl2 L]1.5 I5 (I3 )2 are linked into infinite chains by pairwise hydrogen bonding; the resulting cationic polymers run through channels formed by the extended polyiodide network. [KL2' ]I9 shows a three-dimensional network of puckered cubic cages of I9- ions whose cavities are occupied by the metal cations (section from the structure shown on the right). © 1998 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.