Structural Diversity in 2,2'-[Naphthalene-1,8:4,5-bis(dicarboximide)-'-diyl]-bis(ethylammonium) Iodoplumbates.

Crystallization from solutions containing 2,2'-[naphthalene-1,8:4,5-bis(dicarboximide)-'-diyl]-bis(ethylammonium) diiodide ((NDIC2)I) and PbI has been investigated. Eight different materials are obtained, either by variation of crystallization conditions or by subsequent thermal or solvent-induced transformations. Crystal structures have been determined for five materials. [(NDIC2)PbI(DMF)]·4DMF (DMF = -dimethylformamide) (), [(NDIC2)PbI]·4DMF (), [(NDIC2)PbI]·4NMP (NMP = -methyl-2-pyrrolidone) (), and [(NDIC2)PbI]·2HO () form 1-dimensional (1D) chains consisting of PbI (and, in the case of , PbI(DMF)) octahedra, either solely face-sharing or a mixture of face-sharing and vertex-sharing. The structure of [(NDIC)PbI]·6NMP () contains 0D clusters; these consist of three PbI octahedra and two unusually coordinated lead centers that exhibit three relatively short Pb-I bonds, two very long Pb-I contacts, and η-coordination of an aromatic ring of NDIC2 to the lead. Close contacts between iodide ions and the imide rings of NDIC2 in four of the structures suggest that an iodide-to-NDIC2 charge-transfer interaction may be responsible for the observed red coloration of the materials. The optical and electrical properties of have been studied; its onset of absorption is at 2.0 eV, and its conductivity was measured as 5.4 × 10 ± 1.1 × 10 S m.