Increasing the Structural Rigidity and Quantum Yield of Highly Emissive Hybrid Antimony Chlorides Using a Diverse Set of Solvent Guests

Abstract

Abstract0D 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 (Ph3EtP+), including non‐emissive (Ph3EtP)2Sb2Cl8 and nine (Ph3EtP)2SbCl5‐based emissive compounds, are synthesized and characterized. These emissive compounds are namely, the guest‐free (Ph3EtP)2SbCl5 and (Ph3EtP)2SbCl5·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 ([SbCl4]− and Cl−), leading to the formation of either A2Sb2Cl8 or A2SbCl5. The solvents can be even incorporated into the crystal structure, where stronger interaction with [SbCl5]2− leads to higher temperature of the escape of the solvent. The guest molecules could increase the structural rigidity of [SbCl5]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 [SbCl5]2− deformability, along with enhanced PLQY from 81% in guest‐free to near‐unity in (Ph3EtP)2SbCl5·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.

Negative Thermal Quenching and Self-Trapped Exciton Emission in (R/S-C3H10ON)MnCl3

“…It is important to note that, lattice distortion can significantly impact the emission properties of a material and is often correlated with the STE emission . Previously, many OIH halides were reported, which shows strong bond length distortion (Δ d ) and STE emission (Figure a). ,,− In R / S -APMCl, since two different types of ligands are bonded to the metal center, the bond lengths can differ significantly from each other (Figure b), and hence, polyhedral distortion can be high in this case. Therefore, we have calculated various parameters such as bond length distortion (Δ d ), bond angle variance (σ 2 ), octahedral elongation (λ oct ), octahedral edge deviation (DI), volume discrepancy V (%), and torsional or dihedral distortion (Θ) to quantify the octahedral distortion in both the structures. ,,,− The octahedral distortion parameters are described in Supporting Information, and the calculated values are presented in Table .…”