Optical bandgap anomaly with tuning dimensionality in germanium perovskites: Interplay between quantum confinement and lone pair expression

Li, Xinyu; Tao, Yu; Jiang, Xiaofan; Cai, Guanqun; Gu, Jiazhen; Zheng, Nanlong; Guan, Yan; Zhang, Wenkai; Li, Xiaotong; Su, Jie; Liu, Zhiwei; Bian, Zuqiang; Sun, Junliang; Li, Chen; Fu, Yongping

doi:10.1016/j.chempr.2023.11.011

Cited by 4 publications

References 69 publications

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Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material

Ding,

Zhuang,

Deng

et al. 2024

Chemistry A European J

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The lone pair electrons in the electronic structure of molecules have been a prominent research focus in chemistry for more than a century. Stable s2lone pair electrons significantly influence material properties, including thermoelectric properties, nonlinear optical properties, ferroelectricity, and electro(photo)catalysis.While major advances have been achieved in understanding the influence of lone pair electrons on material characteristics, research on this effect in organic‐inorganic hybrid materials is in its initial stage. In this work, we successfully obtained a novel organic‐inorganic hybrid material incorporating Ge with 4s2 lone pair electrons, (MeHDabco)2[GeBr3]4‐H2O (MeHDabco = N‐methyl‐1,4‐diazabicyclo[2.2.2]octane) (1). Driven by the stereochemically active lone pair electrons on the Ge2+, 1 crystallizes in the noncentrosymmetric space group P21 at room temperature and exhibits good second harmonic generation (SHG) responses. Interestingly, 1 also shows electrocatalytic activity for the hydrogen evolution reaction due to the existence of lone pair electrons on Ge2+ cations. The electrochemical experiment combined with the DFT calculations revealed the lone pair electrons act as both an active site for proton adsorption and facilitate the ionization of water. This work not only emphasizes the important role of lone pair electrons in material properties and functions but also provides new insight for designing novel Ge‐based hybrid materials.

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Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material

Ding,

Zhuang,

Deng

et al. 2024

Chemistry A European J

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Is There an Optimal Spacer Cation for Two-Dimensional Lead Iodide Perovskites?

Gu,

2024

ACS Mater. Au

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Halogen-Dependent Deep-Blue Circularly Polarized Emitters with Ultrahigh-Color-Purity Under High Pressure

Zang,

Sun,

Wang

et al. 2024

Preprint

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Achieving free exciton (FE) emission in low-dimensional (2D, 1D, and 0D) metal halide perovskites is challenging due to the strong electron–phonon coupling effect induced by lead halide octahedral distortion. Herein, the FE emission behaviors of three new 2D chiral perovskites, (R-3-XPEA)2PbBr4 (PEA = phenethylamine, X = F, Cl, Br), were investigated under hydrostatic pressure. (R-3-BrPEA)2PbBr4 and (R-3-ClPEA)2PbBr4 exhibited high color–purity deep-blue circularly polarized luminescence (CPL) dominated by FE at pressures of 1.7 and 2.5 GPa, respectively, whereas (R-3-FPEA)2PbBr4 presented broadband warm-white CPL under high pressure. The structural analysis and theoretical calculation results demonstrated that pressure reduced the penetration depths of R-3-BrPEA+ and R-3-ClPEA+ into [PbBr6]4- inorganic frameworks by strengthening halogen···halogen (Br···Br and Cl···Cl) interactions between organic amines, resulting in smaller [PbBr6]4- octahedral distortion and weaker electron–phonon coupling in (R-3-BrPEA)2PbBr4 and (R-3-ClPEA)2PbBr4. Thus, pressure-driven enhancement of halogen···halogen interactions was responsible for remarkable deep-blue CPL in (R-3-BrPEA)2PbBr4 and (R-3-ClPEA)2PbBr4. Conversely, [PbBr6]4- octahedral distortion and strong electron–phonon coupling could not be effectively suppressed in (R-3-FPEA)2PbBr4 owing to the lack of halogen···halogen interactions, leading to the absence of deep-blue CPL. Our work gives a new insight into the intrinsic structure-property relationship between noncovalent interactions and the ultrahigh-color-purity emission behavior in chiral perovskites.

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Optical bandgap anomaly with tuning dimensionality in germanium perovskites: Interplay between quantum confinement and lone pair expression

Cited by 4 publications

References 69 publications

Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material

Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material

Is There an Optimal Spacer Cation for Two-Dimensional Lead Iodide Perovskites?

Halogen-Dependent Deep-Blue Circularly Polarized Emitters with Ultrahigh-Color-Purity Under High Pressure

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