高圧下におけるキラル2Dペロフスキートのキラル性依存構造変形
Meng-En Sun1, Yonggang Wang2, Fei Wang3
1Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, and College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
Journal of the American Chemical Society
|April 14, 2023
まとめ
チラルのペロブスキットは,非対称な水素結合により,独特の圧力誘発構造変化と負の線形圧縮性 (NLC) を表しています. アキラル・ペロブスキットは,圧力下ではキラリティに依存する効果がない.
科学分野:
- 材料科学
- 固体化学
- クリスタルグラフィー
背景:
- チラルのペロブスキットは,スピントロニックと偏振ベースの光電子学にとって有望である.
- 極端な条件下でのチラリティの移転のメカニズムとその影響は不明である.
- 圧力下でのキラルとアキラルペロブスキットを比較する系統的な研究は稀です.
研究 の 目的:
- エナティオメリックキラルとアキラルペロフスキートを合成し,調査する.
- キラルとアキラルペロブスキートの圧力依存の構造的および光学的差異を調査する.
- 水圧下における物質の振る舞いにおける構造的キラリティの役割を解明する.
主な方法:
- エナティオメール (S/R-3PYEA) PbI4とアキラル (rac-3PYEA) PbI4ペロブスキートの合成.
- 高圧構造の特徴は,X線 difraktionのような技術を使用しています.
- 構造的進化と結合を分析するための第一原理計算.
主要な成果:
- チラル (S/R-3PYEA) PbI4は,バンドギャップの赤いジャンプとピエゾクロミズムで約7.0GPaの圧力誘発の相変化を示している.
- さらに圧縮すると,キラルペロフスキットで負の線形圧縮性 (NLC) が観察される.
- アキラル (rac-3PYEA) PbI4は,バランスのとれた水素結合により,これらのキラリティに依存する移行とNLCを欠いている.
結論:
- キラルな有機カチオンの圧力による傾きは,非対称な水素結合を誘導し,キラルなペロフスキートにおける構造的移行とNLCを誘導する.
- キラル・ペロフスキットの非対称性は[PbI6]4-オクタヘッドの重要な歪みを引き起こす.
- アキラル・ペロブスキットは,バランスのとれた水素結合による対抗力により,これらの現象を呈しない.
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