Two in one: switchable ion conductivity and white light emission integrated in an iodoplumbate-based twin chain hybrid crystal

Abstract

An iodoplumbate-based hybrid, [C7-Apy][PbI3] (1), where C7-Apy(+) = 1-heptyl-4-aminopyridinium, was prepared using a simple solution process. Three sequential phase transitions occur in the range of 402-443 K. In both the lowest and highest temperature phases, hybrid crystal 1 is composed of discrete [Pb2I6]∞ twin chains surrounded by C7-Apy(+) cations. The connectivity between PbI6 octahedra within a [Pb2I6]∞ twin chain and the arrangement of cations are quite difference between the lowest and highest temperature phases. Hybrid crystal 1 shows switchable ion conductivity due to the structural phase transition and white light emission attributed to the broad band semiconductor emission of the twin chain. The former functionality has potential application in ion conductor devices; the single-phase white light emitter is a useful material in low-cost, easily-made, high-efficiency white light-emitting diodes.

Molecular Engineering of Pure 2D Lead‐Iodide Perovskite Solar Absorbers Displaying Reduced Band Gaps and Dielectric Confinement

“…Our observations and conclusions are consistent with preceding reports of iodoplumbates constructed using related pyridinium cations. [44][45][46] From the structuralp arameters listed in Ta bles S1 and S2 (in the Supporting Information), it is clear that the constituent [PbI 6 ] 4À octahedra of 4[PbI 3 ]a re more distorted than those of 3[PbI 3 ]a nd 5[PbI 3 ]. Having discovered that N-alkylated pyridinium cations bearing neutral( i.e.,u ncharged) pendant hydrogen-bond donors are unable to induce formation of 2D perovskite, we sought to incorporate N-ethylammonium functionality.C ombination of the iodide salt of the target dication 6 with PbI 2 afforded the hybrid 6[PbI 4 ], which crystallizes in the monoclinic centrosymmetric space group P12 1 /c12D.…”

“…Room temperature excitation at aw avelength (l ex )o f 335 nm induces weak emissions, centered at approximately 580 nm and extending from 450 to 720 nm, in all of our hybrid 1D materials ( Figure S3 in the Supporting Information, dotted lines).S uch broad emissions have been reported for related pyridinium-templated 1D iodoplumbate systemsa nd were attributed to ac ombination of band edge emissions and energy transfer from the excited state of the inorganic chains to the excited triplet state of the organic components. [44][45][46] However, it is also anticipated that coupling between excitons and phonons can occur in hybrids having distorted inorganic lattices ( Table S2 in the Supporting Information). [24] As such, further investigationsa re neededt oc onfirm the origin of the observed photoluminescence.…”

Morphology-Independent Stable White-Light Emission from Self-Assembled Two-Dimensional Perovskites Driven by Strong Exciton–Phonon Coupling to the Organic Framework

“…[3][4][5][6][7][8][9] In particular, lead (and tin) halide perovskites have shown remarkable color rendition tunability and good quantum efficiencies of photoluminescence emission, establishing them as suitable candidates for LEDs. 4,[10][11][12] Recently, Karunadasa and co-workers reported white-light emission from two instances of two-dimensional (2D) layered perovskites, (N-MEDA)PbX4 (N-MEDA = N 1 -methylethane-1,2-diammonium) and (EDBE)PbX4 (EDBE = 2,2'ethylenedioxy)bis(ethylammonium) with X = Cl or Br. [13][14] The origin of the white-light emission was attributed to electron-phonon coupling and self-trapped excitons.…”

Dual Emissions and Thermochromic Luminescence Behavior of Chloroplumbate Organic–Inorganic Hybrid Crystals

“…This type of twin chain is somewhat similar to the double chain of [CdCl 5 ] 3– in NH 4 CdCl 3 , but there are obvious differences, which mainly concern the Cl – ions adopting three types of coordination modes, including terminal, µ 2 ‐, and µ 4 ‐bridged coordination modes, in the inorganic twin chain of 1 ; however, there are three types of coordination modes, including terminal, µ 2 ‐, and µ 3 ‐bridged coordination modes, in the inorganic double chain of NH 4 CdCl 3 . To the best of our knowledge, this type of octahedral haloplumbate twin chain has been rarely seen in the haloplumbate hybrids , . As shown in Figure c, the charge‐balanced dications occupy the spaces among the haloplumbate twin chains, and the weakly charge‐assisted H bonds appear between the dications and the Cl – ions, with interatomic distances of d Cl10 ··· H20 = 2.744 Å, d Cl11 ··· H8 = 2.695 Å, d Cl12 ··· H5B = 2.915 Å, and d Cl1#1 ··· H7B = 2.844 Å (symmetry codes: #1 = –1 + x, y, z ) at 300 K, which are illustrated in Figure S1a.…”