Elucidating Structure–Property Correlation in Perovskitoid and Antiperovskite Piperidinium Manganese Chloride

Abstract

In the world of semiconductors, organic–inorganic hybrid (OIH) halide perovskite is a new paradigm. Recently, a zealous effort has been made to design new lead-free perovskite-like OIH halides, such as perovskitoids and antiperovskites, for optoelectronic applications. In this context, we have synthesized a perovskitoid compound (Piperidinium)MnCl3 (compound 1) crystallizing in an orthorhombic structure with infinite one-dimensional (1D) chains of MnCl6 octahedra. Interestingly, this compound shows switchable dielectric property governed by an order–disorder structural transition. By controlling the stoichiometry of piperidine, we have synthesized an antiperovskite (Piperidinium)3Cl[MnCl4] (compound 2), the inverse analogue of a perovskite, consisting of zero-dimensional (0D) MnCl4 tetrahedra. This type of organic–inorganic hybrid antiperovskite halide is unique and scarce. Such a dissimilarity in lattice dimensionality and Mn2+ ion coordination ensues fascinating photophysical and magnetic properties. Compound 1 exhibits red emission with a photoluminescence quantum yield (PLQY) of ∼28%. On the other hand, the 0D antiperovskite compound 2 displays green emission with a higher PLQY of 54.5%, thanks to the confinement effect. In addition, the dimensionality of the compounds plays a vital role in the exchange interaction. As a result, compound 1 shows an antiferromagnetic ground state, whereas compound 2 is paramagnetic down to 1.8 K. This emerging structure–property relationship in OIH manganese halides will set the platform for designing new perovskites and antiperovskites.

Electron Spin Decoherence Dynamics in Magnetic Manganese Hybrid Organic–Inorganic Crystals: The Effect of Lattice Dimensionality

“…As exhibited in Figure B–D, 2D, 1D, and 0D manganese hybrids present multiple PL excitation (PLE) peaks from 265 to 540 nm, which can be assigned to the electronic transitions from the ground state ( 6 A 1 (S)) and different excited states ( 4 A 2 (F), 4 T 1 (F), 4 E­(D), 4 T 2 (D), 4 T 2 (D), 4 A 1 , 4 E­(G), 4 T 2 (G), and 4 T 1 (G)) of octahedrally coordinated Mn 2+ ions. These are labeled in the PL spectra according to the Tanabe–Sugano diagram for high-spin d 5 transition metal ions . The PLE spectra accord well with the absorption spectra plotted in Figure S2.…”

Halogen Bond Induced Structural and Photophysical Properties Modification in Organic–Inorganic Hybrid Manganese Halides

“…Manganese­(II)-based OIHs demonstrate attractive structure-governed luminescence properties. − In addition, OIH manganese halides exhibit dielectric, ferroelectric, and multiferroic properties. − Recently, a high piezoelectric response in an OIH halide was observed by the introduction of XB . Nonetheless, reports on XB-mediated structural modification and tunable emission in OIH halides are scarce.…”

Dielectric and optical properties of a new organic–inorganic hybrid phase transition material

“…5b, which is consistent with other works. 38,39 Compound 1 could emit intense green light with UV light exposure; as depicted in Fig. 5c, the excitation (PLE) spectrum showed that it had strong excitation in the visible range at 435 nm, 448 nm and 472 nm corresponding to the transitions of 6 A 1 (S) → 4 A 1 (S), 4 E(G), 6 A 1 (S) → 4 T 2 (G) and 6 A 1 (S) → 4 T 1 (G), respectively.…”