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1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

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Relationship between Pb ion off-centering and lone pair electrons.

Kosuke Kurushima¹, Hiroshi Nakajima², Takahiro Ogata³

¹Toray Research Center, Otsu, Shiga, 520-8567, Japan.

Scientific Reports

|March 19, 2025

Summary

Strontium substitution in lead chromate perovskites reveals lead ion positional distortions. This clarifies the role of lone pair electrons in valence skipping and local lattice distortion in functional materials.

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Area of Science:

Materials Science
Solid-State Chemistry
Crystallography

Background:

Lead-based perovskites synthesized under high pressure show varied functional properties.
Lead chromate (PbCrO3) exhibits unique diffuse scattering and valence skipping, forming both Pb2+ and Pb4+ ions.
The precise spatial arrangement of these lead ions within the crystal structure is not well understood.

Purpose of the Study:

To investigate the distribution and role of lead ions with different valences in PbCrO3.
To understand the impact of strontium (Sr) substitution on the crystal structure and lead ion behavior.
To correlate local structural distortions with observed phenomena like diffuse scattering.

Main Methods:

High-resolution transmission electron microscopy (HRTEM) was employed.
Elemental mapping was performed in conjunction with HRTEM.
Atomistic simulations were utilized to model the lead ion distribution and its effects.

Main Results:

In Pb0.8Sr0.2CrO3, strontium ions were found to occupy a squared lattice.
Lead ions exhibited significant positional distortions within the crystal structure.
Simulations using the experimentally determined lead distribution successfully reproduced the diffuse scattering observed in PbCrO3.

Conclusions:

The positional distortions of lead ions are attributed to the influence of lone pair electrons from s orbitals.
This study provides crucial atomistic insights into the local structures of materials exhibiting valence skipping.
The findings enhance understanding of structure-property relationships in functional perovskites.