Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero‐Dimensional [(C ₆ H ₅ ) ₄ P] ₂ SbCl ₅ Enabled by Pressure‐Induced Lone Pair‐π Interaction

Journal Article · 02 August 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202304494 · OSTI ID:1998003

Luo, Hui ^[1]; Bu, Kejun ^[1]; Yin, Yanfeng ^[2]; Wang, Dong ^[1]; Shi, Cuimi ^[3]; Guo, Songhao ^[1]; Fu, Tonghuan ^[1]; Liang, Jiayuan ^[1]; Liu, Bingyan ^[1]; Zhang, Dongzhou ^[4]; Xu, Liang‐Jin ^[3]; Hu, Qingyang ^[1]; Ding, Yang ^[1]; Jin, Shengye ^[2]; Yang, Wenge ^[1]; Ma, Biwu ^[5]; Lü, Xujie  ^[1]

---

1. Center for High Pressure Science and Technology Advanced Research (HPSTAR) 201203 Shanghai China
2. State Key Laboratory of Molecular Reaction Dynamics and Dynamics Research Center for Energy and Environmental Materials Dalian Institute of Chemical Physics Chinese Academy of Sciences 116023 Dalian Liaoning China
3. State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences 350002 Fuzhou Fujian China
4. Hawaii Institute of Geophysics and Planetology University of Hawaii Manoa Honolulu 96822 Honolulu HI USA
5. Department of Chemistry and Biochemistry Florida State University 32306 Tallahassee FL USA

Abstract Low‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C ₆ H ₅ ) ₄ P] ₂ SbCl ₅ . In situ experimental characterizations and theoretical simulations reveal that the pressure‐induced electronic coupling between the lone‐pair electrons of Sb ³⁺ and the π electrons of benzene ring (lp‐π interaction) serves as an unexpected “bridge” for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp‐π interactions in organic–inorganic hybrid systems.

• Sponsoring Organization: USDOE
• OSTI ID: 1998003
• Journal Information: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 37 Vol. 135; ISSN 0044-8249
• Publisher: Wiley Blackwell (John Wiley & Sons)Copyright Statement
• Country of Publication: Germany
• Language: English