Structural Diversity in 2,2′-[Naphthalene-1,8:4,5-bis(dicarboximide)-<i>N,N</i>′-diyl]-bis(ethylammonium) Iodoplumbates
Marie‐Hélène Tremblay, Andrew M. Zeidell, Sergei Rigin, Colin Tyznik, John Bacsa, Yadong Zhang, Khaled Al Kurdi, Oana D. Jurchescu, Tatiana V. Timofeeva, Stephen Barlow, Seth R. Marder
Abstract
Crystallization from solutions containing 2,2′-[naphthalene-1,8:4,5-bis(dicarboximide)-N,N′-diyl]-bis(ethylammonium) diiodide ((NDIC2)I2) and PbI2 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)2Pb5I14(DMF)2]·4DMF (DMF = N,N-dimethylformamide) (1), [(NDIC2)Pb4I10]·4DMF (3), [(NDIC2)Pb2I6]·4NMP (NMP = N-methyl-2-pyrrolidone) (4), and [(NDIC2)Pb2I6]·2H2O (5) form 1-dimensional (1D) chains consisting of PbI6 (and, in the case of 1, PbI5(DMF)) octahedra, either solely face-sharing or a mixture of face-sharing and vertex-sharing. The structure of [(NDIC2)3Pb5I16]·6NMP (2) contains 0D clusters; these consist of three PbI6 octahedra and two unusually coordinated lead centers that exhibit three relatively short Pb–I bonds, two very long Pb–I contacts, and η2-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 1 have been studied; its onset of absorption is at 2.0 eV, and its conductivity was measured as 5.4 × 10–5 ± 1.1 × 10–5 S m–1.