Pd(II) and Pt(II) complexes of [16]aneS 4 and Pd(II) complexes of cis-(HO) 2 [14]aneS 4 and [9]aneS 3 have been used as templates for the selfassembly of polyiodide ions. The complexes {[M([16]aneS 4 )] 2 I}I 11 (M ϭ Pd, Pt), [Pd(cis-(HO) 2 [14]aneS 4 )](I 3 ) 2 , [Pd([9]aneS 3 ) 2 ](I x ) 2 (x ϭ 3, 5) have been synthesized and structurally characterized. In {[M([16]aneS 4 )] 2 I}I 11 , the polyiodide network consists of fused 14-member polyanion rings made up of interacting "L"-shaped I 5
Ϫ and I Ϫ units; binuclear [([16]aneS 4 )M-I-M([16]aneS 4 )] 3ϩ complex cations featuring a highly unusual linear and symmetric M-I-M moiety are each surrounded by one of these 14-member polyiodide rings in a belt-like fashion. The structures of [Pd(cis-(HO) 2 [14]aneS 4 )](I 3 ) 2 and [Pd ([9]aneS 3 ) 2 ](I 3 ) 2 both feature tri-iodides as counter-anions. In [Pd(cis-(HO) 2 [14]aneS 4 )](I 3 ) 2 , quite asymmetric I 3 Ϫ ions form sinusoidal infinite chains via head-to-tail I 3 Ϫ . . . I 3 Ϫ interactions; these chains run along the (001) direction and are stacked along the (100) direction to form highly puckered anionic layers via I . . . I weak interactions that cross-link the chains. In [Pd([9]aneS 3 ) 2 ](I 3 ) 2 , [Pd([9]aneS 3 ) 2 ] 2ϩ cations are bridged on each side by pairs of symmetric I 3 Ϫ ions through long-range S . . . I contacts to form discrete infinite ribbons that run parallel to the a axis.