Chirality-Dependent Structural Transformation in Chiral 2D Perovskites under High Pressure,Journal of the American Chemical Society

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Chirality-Dependent Structural Transformation in Chiral 2D Perovskites under High Pressure
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-04-14 , DOI: 10.1021/jacs.2c12527
Meng-En Sun ₁ , Yonggang Wang ₂ , Fei Wang ₃ , Jiangang Feng ₄ , Lingrui Wang ₃ , Hanfei Gao ₅ , Gaosong Chen ₁ , Jiazhen Gu ₆ , Yongping Fu ₆ , Kejun Bu ₇ , Tonghuan Fu ₇ , Junlong Li ₈ , Xujie Lü ₇ , Lei Jiang ₅ , Yuchen Wu ₅ , Shuang-Quan Zang ₁

Affiliation

Henan 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.
School of Materials Science and Engineering, Peking University, Beijing 100871, P. R. China.
Key Laboratory of Material Physics, Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, P. R. China.
Department of Electrical and Computer Engineering, National University of Singapore, Singapore 117583, Singapore.
Key Laboratory of Bio-inspired Materials and Interfacial Science, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China.
Beijing National Laboratory for Molecular Science, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China.
Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai 201203, P. R. China.
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Science, Beijing 100049, P. R. China.

Chiral perovskites have attracted considerable attention owing to their potential applications in spintronic- and polarization-based optoelectronic devices. However, the structural chirality/asymmetry transfer mechanism between chiral organic ammoniums and achiral inorganic frameworks is still equivocal, especially under extreme conditions, as the systematic structural differences between chiral and achiral perovskites have been rarely explored. Herein, we successfully synthesized a pair of new enantiomeric chiral perovskite (S/R-3PYEA)PbI₄ (3PYEA²⁺ = C₅NH₅C₂H₄NH₃²⁺) and an achiral perovskite (rac-3PYEA)PbI₄. Hydrostatic pressure was used, for the first time, to systematically investigate the differences in the structural evolution and optical behavior between (S/R-3PYEA)PbI₄ and (rac-3PYEA)PbI₄. At approximately 7.0 GPa, (S/R-3PYEA)PbI₄ exhibits a chirality-dependent structural transformation with a bandgap “red jump” and dramatic piezochromism from translucent red to opaque black. Upon further compression, a previously unreported chirality-induced negative linear compressibility (NLC) is achieved in (S/R-3PYEA)PbI₄. High-pressure structural characterizations and first-principles calculations demonstrate that pressure-driven homodirectional tilting of homochiral ammonium cations strengthens the interactions between S/R-3PYEA²⁺ and Pb–I frameworks, inducing the formation of new asymmetric hydrogen bonds N–H···I–Pb in (S/R-3PYEA)PbI₄. The enhanced asymmetric H-bonding interactions further break the symmetry of (S/R-3PYEA)PbI₄ and trigger a greater degree of in-plane and out-of-plane distortion of [PbI₆]^4– octahedra, which are responsible for chirality-dependent structural phase transition and NLC, respectively. Nevertheless, the balanced H-bonds incurred by equal proportions of S-3PYEA²⁺ and R-3PYEA²⁺ counteract the tilting force, leading to the absence of chirality-dependent structural transition, spectral “red jump”, and NLC in (rac-3PYEA)PbI₄.

中文翻译：

高压下手性二维钙钛矿的手性相关结构转变

手性钙钛矿因其在自旋电子学和偏振基光电器件中的潜在应用而受到广泛关注。然而，手性有机铵和非手性无机骨架之间的结构手性/不对称转移机制仍然模棱两可，特别是在极端条件下，因为很少探索手性和非手性钙钛矿之间的系统结构差异。在此，我们成功合成了一对新型对映体手性钙钛矿( S / R -3PYEA)PbI ₄ (3PYEA ²⁺ = C ₅ NH ₅ C ₂ H ₄ NH ₃²⁺) 和非手性钙钛矿 ( rac -3PYEA)PbI ₄。首次利用静水压力系统研究了( S / R -3PYEA)PbI ₄和( rac -3PYEA)PbI ₄结构演化和光学行为的差异。在大约 7.0 GPa 时，( S / R -3PYEA)PbI ₄表现出依赖于手性的结构转变，具有带隙“红色跳跃”和从半透明红色到不透明黑色的显着压致变色。进一步压缩后，在 ( S /R -3PYEA)PbI ₄。高压结构表征和第一性原理计算表明，压力驱动的纯手性铵阳离子的同向倾斜增强了S / R -3PYEA ²⁺和 Pb–I 框架之间的相互作用，诱导了新的不对称氢键 N–H· 的形成··I–Pb in ( S / R -3PYEA)PbI ₄。增强的不对称氢键相互作用进一步破坏了 ( S / R -3PYEA)PbI _{4的对称性，并引发 [PbI}₆ ] ^4–的更大程度的面内和面外畸变。八面体，分别负责手性相关的结构相变和 NLC。然而，由等比例的S- 3PYEA ²⁺和R -3PYEA ²⁺产生的平衡氢键抵消了倾斜力，导致不存在手性相关的结构转变、光谱“红色跳跃”和 ( rac中的 NLC -3PYEA)PbI ₄。

更新日期：2023-04-14

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