Zero-Dimensional (Piperidinium)2MnBr4: Ring Puckering-Induced Isostructural Transition and Strong Electron–Phonon Coupling-Mediated Self-Trapped Exciton Emission

We report on the synthesis, structure, and photophysical properties of a lead-free organic–inorganic hybrid halide, (Piperidinium)2MnBr4 (PipMBr). It crystallizes in a monoclinic P21/n structure, with isolated MnBr4 tetrahedra representing a zero-dimensional compound. It undergoes a reversible isost...

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Published inInorganic chemistry Vol. 61; no. 29; pp. 11377 - 11386
Main Authors Panda, Debendra Prasad, Swain, Diptikanta, Sundaresan, A.
Format Journal Article
LanguageEnglish
Published American Chemical Society 25.07.2022
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Summary:We report on the synthesis, structure, and photophysical properties of a lead-free organic–inorganic hybrid halide, (Piperidinium)2MnBr4 (PipMBr). It crystallizes in a monoclinic P21/n structure, with isolated MnBr4 tetrahedra representing a zero-dimensional compound. It undergoes a reversible isostructural transition at 422/417 K in the heating/cooling cycle owing to the hydrogen-bonding rearrangement mediated by ring puckering of piperidinium cations. This compound exhibits green emission with a photoluminescence quantum yield of 51%. Interestingly, strong electron-longitudinal optical phonon coupling with γLO of 237 meV is evidenced from the broadening of the temperature-dependent emission linewidth and the Raman spectrum. Such strong electron–phonon coupling and a relatively low Debye temperature (137 K) suggest the self-trapped exciton emission in this compound.
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ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.2c01601