School of Advanced Materials, and Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore560064, India.
Institute of Chemical Technology-IndianOil Odisha Campus, Bhubaneswar751013, India.
Inorg Chem. 2023 Feb 20;62(7):3202-3211. doi: 10.1021/acs.inorgchem.2c04173. Epub 2023 Feb 6.
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)MnCl (compound ) crystallizing in an orthorhombic structure with infinite one-dimensional (1D) chains of MnCl 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)Cl[MnCl] (compound ), the inverse analogue of a perovskite, consisting of zero-dimensional (0D) MnCl tetrahedra. This type of organic-inorganic hybrid antiperovskite halide is unique and scarce. Such a dissimilarity in lattice dimensionality and Mn ion coordination ensues fascinating photophysical and magnetic properties. Compound exhibits red emission with a photoluminescence quantum yield (PLQY) of ∼28%. On the other hand, the 0D antiperovskite compound 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 shows an antiferromagnetic ground state, whereas compound 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.
在半导体领域，有机-无机杂化（OIH）卤化物钙钛矿是一种新的范例。最近，人们积极致力于设计新的无铅钙钛矿类似的 OIH 卤化物，如钙钛矿型和反钙钛矿型，用于光电应用。在这种情况下，我们合成了一种钙钛矿型化合物（哌啶）MnCl（化合物），结晶为正交结构，具有无限的一维（1D）MnCl 八面体链。有趣的是，该化合物表现出由有序-无序结构转变控制的可切换介电性能。通过控制哌啶的化学计量比，我们合成了一种反钙钛矿（哌啶）Cl[MnCl]（化合物），它是钙钛矿的反例，由零维（0D）MnCl 四面体组成。这种类型的有机-无机杂化反钙钛矿卤化物是独特且稀有的。晶格维度和 Mn 离子配位的这种差异导致了迷人的光物理和磁性质。化合物表现出红色发射，光致发光量子产率（PLQY）约为 28%。另一方面，0D 反钙钛矿化合物表现出绿色发射，PLQY 更高，为 54.5%，这要归功于限制效应。此外，化合物的维度在交换相互作用中起着至关重要的作用。结果，化合物表现出反铁磁基态，而化合物在 1.8 K 以下呈顺磁态。OIH 锰卤化物中这种新兴的结构-性质关系将为设计新的钙钛矿和反钙钛矿奠定基础。
