Template Assembly of Polyiodide Networks at Complexed Metal Cations: Synthesis and Structures of [Pd2Cl2([18]aneN2S4)]1.5I5(I3)2 and [K([15]aneO5)2]I9

Abstract

The cations [Pd2Cl2L]2+ and [KL2′+ (L = [18]aneN2S4, L′ =[15]aneO5) have been used as templates for the synthesis of unique three-dimensional polyiodide networks. The metal cations in [Pd2Cl2L]1.5I5(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).