Chiral organic–inorganic lead halide perovskites based on α-alanine

Sirenko, Valerii Y.; Kucheriv, Olesia I.; Naumova, Dina D.; Fesich, I. V.; Linnik, R. P.; Dascălu, Andrei; Shova, Sergiu; Fritsky, Igor O.; Gural'skiy, Il’ya A.

doi:10.1039/d1nj01089a

Cited by 16 publications

(19 citation statements)

References 44 publications

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“…Efforts to expand the functionality of hybrid lead halides have recently included incorporating polar or chiral design elements into the structures. The synthesis of hybrids with chiral ammonium cations has led to noncentrosymmetric crystal structures, some with ferroelectric or second-harmonic generating properties. − Though the metal-centered octahedra found in most hybrid lead halides are nominally of high symmetry, attention has also been given to local symmetry-breaking distortions, including those stemming from expression of lone pairs on the metal centers. , Incorporating metal centers with inherently asymmetric coordination geometries is another, less explored, strategy for introducing local polarity and potentially generating globally noncentrosymmetric materials.…”

Section: Introductionmentioning

confidence: 99%

(C₅H₆N)Pb₂X₅ (X = Cl, Br): Hybrid Lead Halides Based on Seven-Coordinate Pb(II)

et al. 2022

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Hybrid lead halides are a diverse family of compounds, of interest for their optoelectronic properties, that vary in the dimensionality and connectivity of their inorganic substructures. The great majority of these compounds are based on lead-centered octahedra, with few examples featuring inorganic architectures containing higher coordination numbers. Here, we report the synthesis and characterization of a pyridinium lead bromide phase that is based on seven-coordinate Pb(II) centers. Through edge- and face-sharing, the polyhedra form a corrugated, two-dimensional inorganic substructure. Electronic structure calculations were used to examine the band structure and the role of the stereoactive lone pair in the inherently asymmetric, seven-coordinate Pb(II) geometry. For reference, we have visualized the role of the lone pair in the binary halide PbBr2, which also has a seven-coordinate inner ligand sphere. A comparison of the new structure with the limited number of existing hybrid lead halides with similar inorganic architectures highlights the templating role of the organic cation for these compounds. We also contribute characterization and discussion of isomorphic pyridinium lead chloride, which had been deposited in the Cambridge Structural Database but never, to our knowledge, addressed in the literature. The compounds were synthesized using solution conditions and structures determined with single-crystal X-ray diffraction. The materials were also characterized via powder X-ray diffraction, combustion elemental analysis, and diffuse reflectance UV–vis spectroscopy. While the structures reported here are centrosymmetric, the seven-coordinate, capped trigonal prismatic geometry that we have identified is a source of local asymmetry that could be used as a component in designing globally noncentrosymmetric structures.

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Section: Introductionmentioning

confidence: 99%

(C₅H₆N)Pb₂X₅ (X = Cl, Br): Hybrid Lead Halides Based on Seven-Coordinate Pb(II)

et al. 2022

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“…The organic molecules often act as bridging ligands between metal centers and imprint their chiral structural information to final frameworks through coordination bonds. Many homochiral HOMHs and metal–organic frameworks have been developed by this synthetic approach. , In addition, the chiral organic molecules may also serve as structure-directing agents (SDAs) to transfer their chirality to inorganic hosts through hydrogen bonds . It is well-known that hydrogen-bond energies are usually lower than those of coordination bonds.…”

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confidence: 99%

Homochiral Hybrid Organic–Inorganic Cadmium Chlorides Directed by Enantiopure Amino Acids

et al. 2022

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Homochiral cadmium chlorides were prepared under mild conditions using enantiopure amino acids as structure-directing agents. They feature a lacunary hexagonal CdCl2 lattice as well as a one-dimensional perovskite structure. The coexistence of protonated and zwitterionic amino acids between cadmium chloride chains is quite rare. These compounds are nonlinear optically active solids showing a moderate second-harmonic-generation response. Theoretical calculations were performed to reveal the origin of their nonlinear-optical properties.

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“…Chiral α-amino acids are ubiquitous in nature and therefore they are easily accessible precursors. Previously, there were reports on hybrid halide perovskites incorporating chiral α-amino acids such as lysine, 46 ornithine, 46 alanine 47 and proline. 48 However, examples of hybrid perovskites incorporating chiral α-amino acids are still rare.…”

Section: Introductionmentioning

confidence: 99%