Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties

Guan, Junjie; Zheng, Yongshen; Cheng, Puxin; Han, Wenqing; Han, Xiao; Wang, Peihan; Xin, Mingyang; Shi, Rongchao; Xu, Jialiang; Bu, Xian-He

doi:10.1021/jacs.3c09395

“…S6†), again indicating the large anisotropy of its SHG intensity. The polarization ratio ( ρ ) calculated with the formula of ρ = ( I max − I min )/( I max + I min ) 30 can be determined to be 94.9% for 1 and 87.1% for 2 , respectively. The notable polarization ratios for 1 and 2 are comparable to those of hybrid metal halide perovskites such as [ S -3-aminopiperidine]PbI 4 (83%), 48 ( R -MBA)CuBr 2 (97.5%), 11 and DMA 4 [InCl 6 ]Br (99.9%), 30 highlighting the significant anisotropy of the SHG intensity for crystals 1 and 2 .…”

Section: Resultsmentioning

confidence: 99%

“…I > Br > Cl. 27–30 Despite the significant achievements yielded by the above-mentioned strategies, there are still limitations in modulating the physicochemical properties of the hybrid metal halide perovskite family.…”

Section: Introductionmentioning

confidence: 99%

Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)

Zhang,

Ding,

Wang

et al. 2024

Inorg. Chem. Front.

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“…[15] The l oct and s 2 values of � 1 are calculated to be as large as 1.86×10 -5 and 3.24 deg 2 , respectively. [16] With the entry of Cs + ions, the crystal structure of � 1 undergoes a dramatic change. The formed � 2 is still a transparent single crystal on the centimeter scale (with the length over 1.4 cm) but with distinct shape (Figure 1d).…”

Section: Resultsmentioning

confidence: 99%

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

Song,

Wang,

Lu

et al. 2024

Angewandte Chemie

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Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor (glum) is difficult due to usually unmatched electric transition dipole moment (µ) and magnetic transition dipole moment (m) of materials. Herein we tackle this issue by playing a “cascade cationic insertion” trick to achieve strong CPL (with PLQY of ~ 100%) in lead‐free metal halides with high glum values reaching ‐2.3×10‐2 without using any chiral inducers. Achiral solvents of hydrochloric acid (HCl) and N, N‐dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting the perovskite structure to induce the “intrinsic” chirality. Surprisingly, additional insertion of Cs+ cation to substitute partial (CH3)2NH2+ transforms the chiral space group to achiral but the crystal maintains chiroptical activity. Further doping of Sb3+ stimulates strong photoluminescence as a result of self‐trapped excitons (STEs) formation without disturbing the crystal framework. The chiral perovskites of indium‐antimony chlorides embedded on LEDs chips demonstrate promising potential as CPL emitters. Our work presents rare cases of chiroptical activity of highly luminescent perovskites from only achiral building blocks via spontaneous resolution as a result of symmetry breaking.

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“…The authors have cited additional references within the Supporting Information. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] Materials and Methods, Figures S1-26, and Tables S1-6 are included.…”

Section: Supporting Informationmentioning

confidence: 99%

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

Song,

Wang,

Lu

et al. 2024

Angew Chem Int Ed

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Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor (glum) is difficult due to usually unmatched electric transition dipole moment (µ) and magnetic transition dipole moment (m) of materials. Herein we tackle this issue by playing a “cascade cationic insertion” trick to achieve strong CPL (with PLQY of ~ 100%) in lead‐free metal halides with high glum values reaching ‐2.3×10‐2 without using any chiral inducers. Achiral solvents of hydrochloric acid (HCl) and N, N‐dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting the perovskite structure to induce the “intrinsic” chirality. Surprisingly, additional insertion of Cs+ cation to substitute partial (CH3)2NH2+ transforms the chiral space group to achiral but the crystal maintains chiroptical activity. Further doping of Sb3+ stimulates strong photoluminescence as a result of self‐trapped excitons (STEs) formation without disturbing the crystal framework. The chiral perovskites of indium‐antimony chlorides embedded on LEDs chips demonstrate promising potential as CPL emitters. Our work presents rare cases of chiroptical activity of highly luminescent perovskites from only achiral building blocks via spontaneous resolution as a result of symmetry breaking.

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Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties

Cited by 19 publications

References 95 publications

Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)

Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

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Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties

Cited by 19 publications

References 95 publications

Achieving strong second harmonic generation effects induced via dimensional increase of PbX6 octahedra and halogen substitutes in (C10H11N3)PbX4 (X = Cl or Br)

Achieving strong second harmonic generation effects induced via dimensional increase of PbX6 octahedra and halogen substitutes in (C10H11N3)PbX4 (X = Cl or Br)

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

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Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)

Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)