Structural diversity in hybrid lead halides templated by 4-methylimidazolium

Elliott, Clement; McNulty, Jason A.; Cordes, David B.; Slawin, Alexandra M. Z.; Lightfoot, Philip

doi:10.1016/j.jssc.2021.122466

Cited by 9 publications

(28 citation statements)

References 46 publications

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“…The crystal structure of IMPbBr 3 , solved at 173 K, has already been reported. 39 It is a 3D derivative of the perovskite structure built of face-sharing PbBr 6 octahedra, which additionally share the free corners to form a three-dimensional network. This so-called 4H-hexagonal polytype develops channels propagating along the c -direction, which are occupied by protonated amines.…”

Section: Resultsmentioning

confidence: 99%

“…Elliot et al reported the low-temperature (LT) structure of the orthorhombic Pnma symmetry. 39 Due to the fact that this compound exhibits two phase transitions at 200 and 240 K, we decided to follow the thermal evolution of its structure. Below, we summarize the results.…”

Section: Resultsmentioning

confidence: 99%

“… 38 Regarding imidazolium lead bromides, only one compound was reported in the literature with the chemical composition IMPbBr 3 . 39 Its crystal structure, solved at 173 K, is orthorhombic, space group Pnma , and it adopts a distorted 4H perovskite-like structure with face- and corner-sharing octahedra. 39 …”

Section: Introductionmentioning

confidence: 99%

“… 39 Its crystal structure, solved at 173 K, is orthorhombic, space group Pnma , and it adopts a distorted 4H perovskite-like structure with face- and corner-sharing octahedra. 39 …”

Section: Introductionmentioning

confidence: 99%

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Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

et al. 2022

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Hybrid organic–inorganic lead halide perovskites have emerged as promising materials for various applications, including solar cells, light-emitting devices, dielectrics, and optical switches. In this work, we report the synthesis, crystal structures, and linear and nonlinear optical as well as dielectric properties of three imidazolium lead bromides, IMPbBr 3 , IM 2 PbBr 4 , and IM 3 PbBr 5 (IM + = imidazolium). We show that these compounds exhibit three distinct structure types. IMPbBr 3 crystallizes in the 4H-hexagonal perovskite structure with face- and corner-shared PbBr 6 octahedra (space group P 6 3 / mmc at 295 K), IM 2 PbBr 4 adopts a one-dimensional (1D) double-chain structure with edge-shared octahedra (space group P 1̅ at 295 K), while IM 3 PbBr 5 crystallizes in the 1D single-chain structure with corner-shared PbBr 6 octahedra (space group P 1̅ at 295 K). All compounds exhibit two structural phase transitions, and the lowest temperature phases of IMPbBr 3 and IM 3 PbBr 5 are noncentrosymmetric (space groups Pna 2 1 at 190 K and P 1 at 100 K, respectively), as confirmed by measurements of second-harmonic generation (SHG) activity. X-ray diffraction and thermal and Raman studies demonstrate that the phase transitions feature an order–disorder mechanism. The only exception is the isostructural P 1̅ to P 1̅ phase transition at 141 K in IM 2 PbBr 4 , which is of a displacive type. Dielectric studies reveal that IMPbBr 3 is a switchable dielectric material, whereas IM 3 PbBr 5 is an improper ferroelectric. All compounds exhibit broadband, highly shifted Stokes emissions. Features of these emissions, i.e. , band gap and excitonic absorption, are discussed in relation to the different structures of each composition.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“… 39 Its crystal structure, solved at 173 K, is orthorhombic, space group Pnma , and it adopts a distorted 4H perovskite-like structure with face- and corner-sharing octahedra. 39 …”

Section: Introductionmentioning

confidence: 99%

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Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

et al. 2022

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“…[22][23][24] Reported are 1D perovskitoids, [25] but as well 2D and 3D structures are already available. [26][27][28] The electronic structure of the conduction and valence band is influenced by both constituents, the inorganic and the organic. [19,29] Due to the confinement of the charge carriers, the inorganic layers behave like quantum wells.…”

Section: Introductionmentioning

confidence: 99%

Design of Active Defects in Semiconductors: 3D Electron Diffraction Revealed Novel Organometallic Lead Bromide Phases Containing Ferrocene as Redox Switches

Fillafer

Kuper

Schaate

et al. 2022

Adv Funct Materials

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Once the optical, electronic, or photocatalytic properties of a semiconductor are set by adjusting composition, crystal phase, and morphology, one cannot change them anymore, respectively, on demand. Materials enabling postsynthetic and reversible switching of features such as absorption coefficient, bandgap, or charge carrier dynamics are highly desired. Hybrid perovskites facilitate exceptional possibilities for progress in the field of smart semiconductors because active organic molecules become an integral constituent of the crystalline structure. This paper reports the integration of ferrocene ligands into semiconducting 2D phases based on lead bromide. The complex crystal structures of the resulting, novel ferrovskite (≃ ferrocene perovskite) phases are determined by 3D electron diffraction. The ferrocene ligands exhibit strong structure‐directing effects on the 2D hybrid phases, which is why the formation of exotic types of face‐ and edge‐sharing lead bromide octahedra is observed. The bandgap of the materials ranges from 3.06 up to 3.51 eV, depending on the connectivity of the octahedra. By deploying the redox features of ferrocene, one can create defect states or even a defect band leading to control over the direction of exciton migration and energy transport in the semiconductor, enabling fluorescence via indirect to direct gap transition.

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Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H₂O Vapor Sorption

Azmy

Angeli

et al. 2023

Angewandte Chemie

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In this work we report a strategy for generating porosity in hybrid metal halide materials using molecular cages that serve as both structure‐directing agents and counter‐cations. Reaction of the [2.2.2] cryptand (DHS) linker with PbII in acidic media gave rise to the first porous and water‐stable 2D metal halide semiconductor (DHS)2Pb5Br14. The corresponding material is stable in water for a year, while gas and vapor‐sorption studies revealed that it can selectively and reversibly adsorb H2O and D2O at room temperature (RT). Solid‐state NMR measurements and DFT calculations verified the incorporation of H2O and D2O in the organic linker cavities and shed light on their molecular configuration. In addition to porosity, the material exhibits broad light emission centered at 617 nm with a full width at half‐maximum (FWHM) of 284 nm (0.96 eV). The recorded water stability is unparalleled for hybrid metal halide and perovskite materials, while the generation of porosity opens new pathways towards unexplored applications (e.g. solid‐state batteries) for this class of hybrid semiconductors.

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Structural diversity in hybrid lead halides templated by 4-methylimidazolium

Cited by 9 publications

References 46 publications

Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

Design of Active Defects in Semiconductors: 3D Electron Diffraction Revealed Novel Organometallic Lead Bromide Phases Containing Ferrocene as Redox Switches

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H₂O Vapor Sorption

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Structural diversity in hybrid lead halides templated by 4-methylimidazolium

Cited by 9 publications

References 46 publications

Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

Effect of Dimensionality on Photoluminescence and Dielectric Properties of Imidazolium Lead Bromides

Design of Active Defects in Semiconductors: 3D Electron Diffraction Revealed Novel Organometallic Lead Bromide Phases Containing Ferrocene as Redox Switches

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H2O Vapor Sorption

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Product

Resources

About

Porous and Water Stable 2D Hybrid Metal Halide with Broad Light Emission and Selective H₂O Vapor Sorption