[PPh3H]2[SbCl5]: A Zero-Dimensional Hybrid Metal Halide with a Supramolecular Framework and Stable Dual-Band Emission

Authors：Peng, Ying-Chen; Zhou, Sheng-Hua; Jin, Jian-Ce; Zhuang, Ting-Hui; Gong, Liao-Kuo; Lin, Hao-Wei; Wang, Ze-Ping^*; Du, Ke-Zhao^*; Huang, Xiao-Ying^*

Source：Journal of Physical Chemistry C, 2022.

DOI：10.1021/acs.jpcc.2c05299

• SELF-TRAPPED EXCITONS
• WHITE-LIGHT EMISSION
• QUANTUM EFFICIENCY
• MOLECULAR-DYNAMICS
• ANTIMONY HALIDE
• PHOTOLUMINESCENCE
• PEROVSKITES
• LUMINESCENCE
• CRYSTAL
• BI

Zero-dimensional (0D) organic-inorganic metal hal -ides (OIMHs) have attracted tremendous attention due to their fascinating optoelectronic properties. Herein, we report an antimony-(III)-based 0D OIMH of [PPh3H]2[SbCl5] comprising discrete [SbCl5]2- pyramids and protonated triphenylphosphine (PPh3H) cations with a low charge density. Abundant supramolecular interactions including C-H center dot center dot center dot Cl and rare P-H center dot center dot center dot Cl hydrogen bonds and C-H center dot center dot center dot pi and anion center dot center dot center dot pi interactions lead to a three-dimensional (3D) supramolecular framework structure of [PPh3H]2[SbCl5]. Photophysical characterizations indicate that [PPh3H]2[SbCl5] has singlet/triplet dual-band emission. The intersystem crossing between the single and triplet states is tunable upon changing the temperature. Analyses of the Huang-Rhys factor (S), exciton activation energy (Ea), and electron-phonon coupling energy (Gamma op) verify that the soft lattice and strong electron-phonon coupling result in the broad emission of [PPh3H]2[SbCl5], while the excited-state reorganization of the [SbCl5]2- pyramid leads to a large Stokes shift. DFT calculations help provide a deep understanding on the optical property of [PPh3H]2[SbCl5]. The title compound could remain stable for more than 1 year without the obvious decay of emission, which may be related to the rigid 3D supramolecular framework.

• Institution
  Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences; Graduate University of Chinese Academy of Sciences