Reactivity of Polyiodides Towards 1,3‐Bis(4‐pyridyl)propane (bpp): A New CuI Cluster Polycatenane Framework and a Novel 2D AgI Cluster Motif

Abstract

Abstract The solution‐phase reactions of metal iodides or iodine with 1,3‐bis(4‐pyridyl)propane (bpp) yields four new organic–inorganic hybrid frameworks, namely [(CuI) 4 (bpp) 4 ] n ( 1 ), [(AgI) 6 (bpp)] n ( 2 ), [PbI 2 (bpp)] n ( 3 ), and [I 3 (bppH)] ( 4 ), each of which adopts a different structural motif. For example, complex 1 is a 2D “open” coordination polymeric cluster consisting of a CuI 2 Cu rhomboid cluster core coordinated by anti‐anti and anti‐gauche bpp interactions to produce an interpenetrating 2D (4,4) polycatenane net; 2 is a novel bpp inclusion compound with a unique 2D polymeric hexagonal prism‐shaped [Ag 6 I 6 ] n cluster motif; compound 3 is also a 2D “open” supramolecular cluster made from [PbI 2 ] n “ribbons” and bpp bridges; compound 4 is a triiodide made up of organic [bppH] + cations and a I 3 – anion chain. The clusters 1 – 3 obtained from the reaction between polyiodide complexes and an organic ligand suggest that this simple synthetic approach is likely to be applicable to the construction of polymeric clusters. The third‐order NLO effects of 1 were studied by Z‐scan techniques. The polymeric cluster exhibits good nonlinearities and the effective third‐order NLO refractive index ( n 2 ) value is 2.56 × 10 –12 esu which is comparable to those of most cluster monomers and polymers. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)