Increasing the Structural Rigidity and Quantum Yield of Highly Emissive Hybrid Antimony Chlorides Using a Diverse Set of Solvent Guests
Peiran Xie, Pan Wang, Zhou Jiaqian, Zhu Guo, Lingling Mao
Abstract
Abstract 0D organic–inorganic antimony halides have attracted increasing attention due to the non‐toxicity, high stability, and superior photoluminescence quantum yield (PLQY). Here, a series of hybrid antimony chlorides with the same organic cation ethyltriphenylphosphonium (Ph 3 EtP + ), including non‐emissive (Ph 3 EtP) 2 Sb 2 Cl 8 and nine (Ph 3 EtP) 2 SbCl 5 ‐based emissive compounds, are synthesized and characterized. These emissive compounds are namely, the guest‐free (Ph 3 EtP) 2 SbCl 5 and (Ph 3 EtP) 2 SbCl 5 ·guest (guest = glycol, acetic acid, methanol, ethanol, n‐propanol, i‐propanol, acetone, and acetonitrile). The solvent used can alter the coordination mode of Sb because the solvation effect affects the reactivity of the anions ([SbCl 4 ] − and Cl − ), leading to the formation of either A 2 Sb 2 Cl 8 or A 2 SbCl 5 . The solvents can be even incorporated into the crystal structure, where stronger interaction with [SbCl 5 ] 2− leads to higher temperature of the escape of the solvent. The guest molecules could increase the structural rigidity of [SbCl 5 ] 2− via hydrogen bonding and dipole–dipole interactions, which tends to reduce the room‐temperature photoluminescence (PL) Stokes shift and temperature‐dependent PL shift by decreasing the [SbCl 5 ] 2− deformability, along with enhanced PLQY from 81% in guest‐free to near‐unity in (Ph 3 EtP) 2 SbCl 5 ·glycol. This work shows that targeted synthesis and diversified choices of solvents provide an efficient tool to generate steady variations in hybrid emissive materials for optoelectronics.