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

Abstract

Crystallization from solutions containing 2,2′-[naphthalene-1,8:4,5bis(dicarboximide)-N,N′-diyl]-bis(ethylammonium) diiodide ((NDIC2)I 2 ) and PbI 2 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. 5) form 1-dimensional (1D) chains consisting of PbI 6 (and, in the case of 1, PbI 5 (DMF)) octahedra, either solely facesharing or a mixture of face-sharing and vertex-sharing. The structure of [(NDIC 2 ) 3 Pb 5 I 16 ]•6NMP (2) contains 0D clusters; these consist of three PbI 6 octahedra and two unusually coordinated lead centers that exhibit three relatively short Pb−I bonds, two very long Pb−I contacts, and η 2 -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 .

Halogen-Manipulated Interfacial Charge Transport of π-Conjugated Molecule-Lead Halide Hybrids

“…With the increase of Br content, the lamellar structure gradually becomes blurred and the crystal surface becomes smoother. For crystal 1 , the average Pb–I bond length in the inorganic chain is 3.233 Å (3.200–3.261 Å), which is the typical Pb–I bond lengths in perovskites and perovskite-like materials . The in-plane bending angle in the face-sharing octahedron is 179.7° (Figure S8), suggesting the linear conformation of the 1D inorganic chain.…”

“…For crystal 1, the average Pb−I bond length in the inorganic chain is 3.233 Å (3.200−3.261 Å), which is the typical Pb−I bond lengths in perovskites and perovskite-like materials. 31 The in-plane bending angle in the face-sharing octahedron is 179.7°(Figure S8), suggesting the linear conformation of the 1D inorganic chain. Adjacent NDIA connects by the intermolecular H-bonds formed between the hydrogen on the end of the n-butylamine with oxygen anhydride and nitrogen amide (Figure S9b) but without direct π−π stacking.…”

Interlayer Triplet-Sensitized Luminescence in Layered Two-Dimensional Hybrid Metal-Halide Perovskites

“…Bulkier cations have also been shown to induce distortions in the metal-halide lattice that affect the bandgap and other energetic properties . Furthermore, researchers have found that certain bulky cations tend to stabilize in even lower dimensional perovskite-like structures (i.e., corner-sharing metal-halide octahedron), such as 1D wires or 0D clusters. − While these lower dimensional structures possess interesting and useful properties of their own (e.g., strong quantum confinement, size-dependent properties, and exotic structural possibilities), they can also have undesirable properties such as rapid self-trapping of excitons and shorter excited-state lifetimes . Because of the structural limitations of the layered 2D MHP lattice, the majority of organic cations that have been explored so far are either minimally branched alkyl chains (as long as eight units have been reported) or small aromatics like acenes and thiophenes.…”

Naphthalenediimide Cations Inhibit 2D Perovskite Formation and Facilitate Subpicosecond Electron Transfer

“…35−37 A recent study demonstrated numerous 0D and 1D structures formed from PbI 2 and NDIC2, where the structures could be altered by crystallization conditions or thermal-and solvent-induced transformations. 38 However, no 2D PQW structures or materials including both NDIC2 and other organic cations have yet been reported. We fabricated thin films of higher n perovskites containing NDIC2 molecules to study how they affect PQW formation, width distribution, structure, spatial ordering, and photoexcited carrier dynamics of the hybrid system.…”