Photophysical Behavior of Triethylmethylammonium Tetrabromoferrate(III) under High Pressure

Nakagawa, Takeshi; Ding, Yang; Bu, Kejun; Lü, Xujie; Liu, Haozhe; Moliterni, Anna; Popović, Jasminka; Mihalik, Marian; Jagličić, Zvonko; Mihalik, Matúš; Vrankić, Martina (2023) Photophysical Behavior of Triethylmethylammonium Tetrabromoferrate(III) under High Pressure. Inorganic Chemistry, 62 (48). pp. 19527-19541. ISSN 0020-1669

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Abstract

The pressure-induced properties of Hybrid Organic-Inorganic Ferroelectrics (HOIFs) with tunable structures and selectable organic and inorganic components are important for device fabrication. However, given the structural complexity of polycrystalline HOIFs and the limited resolution of pressure data, resolving the structure-property puzzle has so far been the exception rather than the rule. With this in mind, we present a collection of in situ high-pressure data measured for the triethylmethylammonium tetrabromoferrate(III), ([N(C2H5)3CH3][FeBr4]) (EMAFB) by unraveling its flexible physical and photophysical behavior up to 80 GPa. Pressure-driven X-ray diffraction and Raman spectroscopy disclose its soft and reversible structural distortion, creating room for delicate band gap modulation. During compression, orange turns dark red at 2 GPa, and further compression results in piezochromism, leading to opaque black, while decompressed EMAFB appears in an orange hue. Assuming that the mechanical softness of EMAFB is the basis for reversible piezochromic control, we present alternations in the electronic landscape leading to a 1.22 eV band narrowing at 20.3 GPa, while maintaining the semiconducting character at 72 GPa. The EMAFB exhibits an emission enhancement, manifested by an increase of photoluminescence up to 17.3 GPa, correlating with the onsets of structural distortion and amorphization. The stimuli-responsive behavior of EMAFB, exhibiting a stress-activated modification of the electronic structure, can enrich the physical library of HOIFs suitable for pressure-sensing technologies.

Item Type:	Article
Uncontrolled Keywords:	high pressure, hybrid organic-inorganic molecular ferroelectrics; powder X-ray diffraction; crystal structure solution; phase transition; piezochromism
Subjects:	NATURAL SCIENCES > Physics > Condensed Matter Physics NATURAL SCIENCES > Chemistry > Inorganic Chemistry
Divisions:	Division of Materials Physics
Depositing User:	Martina Vrankić
Date Deposited:	15 Feb 2024 13:44
URI:	http://fulir.irb.hr/id/eprint/8586
DOI:	10.1021/acs.inorgchem.3c02607

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