Guest-Induced Reversible Phase Transformation of Organic–Inorganic Phenylpiperazinium Antimony (III) Chlorides with Solvatochromic Photoluminescence

Abstract

Antimony halide hybrids have been recently revealed to show reversible solvent-induced phase transformation along with solvatochromic photoluminescence (PL). However, the effects of guest molecules on such phase transformation are not yet well understood due to metastable solvent-induced phases. Here, we report the synthesis of 1-phenylpiperazinium (PhPi)-incorporated antimony chloride hybrids ((PhPi)2SbCl7·xH2O) with a guest H2O-mediated hydrogen bonding network. Upon removing H2O molecules through vacuum treatment or solvent induction, red-emissive (PhPi)2SbCl7·xH2O with a PL quantum yield (QY) of 32% is transformed into two yellow-emissive isomers (PhPi)2SbCl7-V (PL QY: 9%) or (PhPi)2SbCl7-S (PL QY: 95%), which can be reversibly transformed into (PhPi)2SbCl7·xH2O by placing in open air. Due to more compact and rigid structures that suppress octahedral distortion, smaller Stokes shifts are observed for both (PhPi)2SbCl7-V (1.41 eV) and (PhPi)2SbCl7-S (1.35 eV), consistent with density function theory calculations that (PhPi)2SbCl7·xH2O exhibits the largest distortion at excited states. Additionally, compared to poorly emissive (PhPi)2SbCl7-V, (PhPi)2SbCl7-S with near-unity QY is attributed to the Jahn–Teller-like deformation of excited states and a large thermal quenching barrier. Our findings highlight the role of guest molecules in tuning [SbCl6] octahedral distortion to enhance the luminescence efficiency of Sb-based halides.

High quantum yield of In‐based halide perovskites for white light emission and flexible x‐ray scintillators

“…The PL emissions of MA 4 In 1– x Sb x Cl 7 followed a mono‐exponential decay, as indicated in Figure 1F. The average decay lifetime of MA 4 In 1– x Sb x Cl 7 reaches the microsecond level, which is the same as the lifetime of Sb‐based metal halides reported previously 50 . The transient PL results demonstrate average PL decay values of 6.0, 6.1, 5.9, and 5.7 μs for x = 5, 10, and 20, 30, respectively, coinciding to this change of PLQY.…”

Oxidation-induced phase transformations of hybrid tin bromide single crystals enable the occurrence of second-harmonic generation

“…8,15 Recently, there have been some reports on the phase transformation research of manganese (Mn) and antimony (Sb)-based hybrid materials, which focused on changes in the coordination number of Mn 2+ and the doping of Sb 3+ to regulate the emission wavelength. [16][17][18] In addition, Sb 3+ doped organic-inorganic hybrid material exhibits an emission response to a specific organic solvent. 19 Until now, there have been few reports on phase transformations of lead and leadfree organic-inorganic/all-inorganic materials.…”

Orange/cyan emissive sensors of Sb3+ for probing water via reversible phase transformation in rare-earth-based perovskite crystals

“…1 The emissive light of Sb 3+ can be sensitively switched between red/yellow in zero-dimensional (0D) halide single crystals (PPZ) 2 SbCl 7 •5H 2 O (PPZ = 1-phenylpiperazine) and Cs 2 InBr 5 •H 2 O:Sb 3+ ascribed to the insertion/removal of the water molecules into/from the matrixes. [2][3][4] Environmentally friendly alternatives free of Pb and organics, and possessing high PLQYs and detection sensitivity, are still in demand in the growing field for application in sensors and anti-counterfeiting.…”